Compounds derived from polyanhydride resins with film-forming, UV-absorbing, and photostablizing properties, compositions containing same, and methods of using the same

ABSTRACT

Polymers containing one or more crylene and fluorene moieties attached to the polymer backbone, sunscreen compositions including a mixture of a photoactive compound and a polymer containing one or more crylene and fluorene moieties attached to the polymer backbone are described herein. Also disclosed are methods for stabilizing a sunscreen composition and methods of filtering out ultra-violet light from a substrate by the addition of one or more of the foregoing polymers, and methods of waterproofing and forming a film with one or more of the foregoing polymer are described herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to compounds, and methods to increase theUV-absorbance, water resistance, and photostability of a variety ofcompositions. More particularly, the invention relates tocyanodiphenylacrylate (“Crylene”) and/or cyanofluorenylidene acetate(“Fluorene”) polymer compounds and compositions containing the same, andmethods of using them that include a method of protecting a materialfrom ultra-violet radiation, a method of waterproofing, a method offorming a film, and a method of photostabilizing a photounstablecompound.

2. Brief Description of Related Technology

It is well known that ultraviolet radiation (light) having a wavelengthfrom about 280 nm or 290 nm to about 320 nm (UV-B) is harmful to humanskin, causing burns that are detrimental to the development of a goodsun tan. UV-A radiation (about 320 nm to about 400 nm), while producingtanning of the skin, also can cause damage, particularly to verylightly-colored or sensitive skin, leading to reduction of skinelasticity and wrinkles. Therefore, a sunscreen composition for use onhuman skin preferably includes both a UV-A and a UV-B filter to preventmost of the sunlight within the full range of about 280 nm or 290 nm toabout 400 nm from damaging human skin.

Ultraviolet radiation from the sun or artificial sources can also causeharm to coatings containing photoactive substances, such as photoactivepigments and dyes, by breaking down chemical bonds in the structure of acomponent such as a polymer, a pigment, or a dye. This photodegradationcan lead to color fading, loss of gloss; and loss of physical andprotective properties of a coating. Photodegradation can take place inseveral steps which include one or more components of a coatingabsorbing UV radiation. The absorbed radiation can excite the absorbingmolecules and raise them to a higher energy level, which can be veryreactive. If the molecule cannot be relaxed, bond cleavage and theformation of free radicals will occur. These free radicals can attackone or more color molecules and/or a polymer backbone and form more freeradicals.

UV-A and UV-B filters can also be used to absorb UV radiation to protecta pigmented coating. The UV-B filters that are most widely used in theU.S. in commercial sunscreen compositions are paramethoxycinnamic acidesters, such as 2-ethylhexyl paramethoxycinnamate, commonly referred toas octyl methoxycinnamate or PARSOL MCX; octyl salicylate; andoxybenzone.

The organic UV-A filters most commonly used in commercial sunscreencompositions are the dibenzoylmethane derivatives, particularly4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane (also calledavobenzone, sold under the brand name PARSOL 1789). Otherdibenzoylmethane derivatives described as UV-A filters are disclosed inU.S. Pat. Nos. 4,489,057, 4,387,089 and 4,562,067, the disclosures ofwhich are hereby incorporated herein by reference. It is also well knownthat the above described UV-A filters, particularly the dibenzoylmethanederivatives, can suffer from rapid photochemical degradation, when usedalone or when combined with the above-described most commercially usedUV-B filters.

Typically, the above-described UV-B filters are combined with the abovedescribed UV-A filters in a solution with other lipophilic or oilyingredients. This solution of oily ingredients, known to formulators ofcosmetic products including sunscreens as the “oil phase,” is typically,but not necessarily, dispersed with the help of emulsifiers andstabilizers into an aqueous solution composed primarily of water, tomake an emulsion which becomes a final cream or lotion form of asunscreen composition.

The performance of a photoactive compound or a combination ofphotoactive compounds in a sunscreen composition has been extremelydifficult to predict based on the levels of photoactive compounds in theformulation, particularly when the formulation includes one or morephotoactive compounds that suffer from relatively rapidphotodegradation, such as avobenzone. Because of this, each formulationhas required expensive laboratory testing to determine the UVabsorbance, as a function of time (quantity) of exposure of theformulation to UV radiation. Moreover, a particularly difficult problemis presented when one photoactive compound in a sunscreen compositionacts to increase the rate of photodegradation of another photoactivecompound in the composition. This can be accomplished in a number orways, including a bimolecular reaction between two photoactive compoundsand a lowering of the threshold energy needed to raise a photoactivecompound to its excited state. For example, when avobenzone is combinedwith octyl methoxycinnamate a bimolecular pathway leads to the rapidphotodegradation of both the dibenzoylmethane derivative and the octylmethoxycinnamate.

Methods and compositions for stabilizing photoactive compounds, such asdibenzoylmethane derivatives, with the use of octocrylene and fluoreneare described in the commonly-assigned U.S. Pat. Nos. 5,993,789,6,113,931, 6,126,925, and 6,284,916, the disclosures of which are herebyincorporated herein by reference. Other methods of stabilizing adibenzoylmethane derivative include the addition of anα-cyano-β,β-diphenylacrylate compound to a sunscreen compositionincluding a dibenzoylmethane derivative. See, Deflandre et al, U.S. Pat.No. 5,576,354 and Gonzenbach et al., U.S. Pat. No. 6,033,649.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of the absorbance of a sunscreen composition thatincludes 2% Octadecene/Crylene maleate copolymer as the onlyUV-absorbing compound, from a wavelength of 280 nm to 400 nm.

FIG. 2 is a graph of the absorbance of a sunscreens composition thatincludes 2% Octadecene/Crylene maleate copolymer as the onlyUV-absorbing compound, a sunscreen composition (with UV-absorbingcompounds) that does not include Octadecene/Crylene maleate copolymer,and a sunscreen composition including 2% of the Octadecene/Crylenemaleate copolymer and other UV-absorbing compounds, from a wavelength of280 nm to 400 nm.

FIG. 3 is a graph of the original absorbance of a sunscreen compositionthat does not include Octadecene/Crylene maleate copolymer from awavelength of 280 nm to 400 nm and after the composition has beenexposed to 35 MED.

FIG. 4 is a graph of the original absorbance of a sunscreen compositionthat includes 2% of the Octadecene/Crylene maleate copolymer from awavelength of 280 nm to 400 nm and after the composition has beenexposed to 35 MED.

FIG. 5 is a graph of the original absorbance of a sunscreen compositionincluding 2% Octadecene/Crylene maleate copolymer, and a sunscreencomposition not including Octadecene/Crylene maleate copolymer, whereinthe absorbance is measured from a wavelength of 280 nm to 400 nm andafter the compositions have been exposed to 35 MED.

FIG. 6 is a graph of the absorbance of a sunscreen composition that doesnot include Octadecene/Crylene maleate copolymer, from a wavelength of280 nm to 400 nm.

FIG. 7 is a graph of the absorbance of a sunscreen composition thatincludes 2% Octadecene/Crylene maleate copolymer, from a wavelength of280 nm to 400 nm.

FIG. 8 is a graph of the original absorbance of a sunscreen compositionthat did not include the Octadecene/Crylene maleate copolymer, measuringthe absorbance from a wavelength of 280 nm to 400 nm, and after thecomposition was immersed in water for 40 minutes.

FIG. 9 is a graph of the original absorbance of a sunscreen compositionthat includes 2% of the Octadecene/Crylene maleate copolymer, measuringthe absorbance from a wavelength of 280 nm to 400 nm, and after thecomposition was immersed in water for 40 minutes.

FIG. 10 is a graph of the original absorbance of a sunscreen compositionthat includes 2% of the Octadecene/Crylene maleate copolymer, and asunscreen composition that did not include the Octadecene/Crylenemaleate copolymer, measuring the absorbance from a wavelength of 280 nmto 400 nm, and after the compositions were immersed in water for 40minutes.

SUMMARY

One aspect of the compounds, compositions, and methods disclosed hereinis to provide a polymeric compound having a crylene moiety(2-cyano-3,3-diphenylacrylic acid) attached to the polymer backbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a sunscreen composition that includes aUV-absorbing polymeric compound having a crylene moiety(2-cyano-3,3-diphenylacrylic acid) attached to the polymer backbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method of reducing or eliminating an amount ofultra-violet light that contacts a substrate by disposing between thesource of ultra-violet light and the substrate, or applying to thesubstrate a polymeric compound having a crylene moiety(2-cyano-3,3-diphenylacrylic acid) attached to the polymer backbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method of waterproofing a substrate surface byapplying thereto a polymeric compound having a crylene moiety(2-cyano-3,3-diphenylacrylic acid) attached to the polymer backbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method of protecting a photodegradable materialagainst photodegradation by applying thereto a polymeric compound havinga crylene moiety (2-cyano-3,3-diphenylacrylic acid) attached to thepolymer backbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method of forming a UV-absorbing film on asubstrate surface by applying thereto film or coating containing apolymeric compound having a crylene moiety (2-cyano-3,3-diphenylacrylicacid) attached to the polymer backbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method for photostabilizing a sunscreencomposition including a photoactive compound by the addition of aphotostabilizing effective amount of a polymeric compound having acrylene moiety (2-cyano-3,3-diphenylacrylic acid) attached to thepolymer backbone.

Yet another aspect of the compounds, compositions, and methods disclosedherein is to provide a polymeric compound having a fluorene moiety(cyano(9H-fluoren-9-ylidene)acetic acid) attached to the polymerbackbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a sunscreen composition that includes a polymericcompound having a fluorene moiety (cyano(9H-fluoren-9-ylidene)aceticacid) attached to the polymer backbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method of reducing or eliminating an amount ofultra-violet light that contacts a substrate by disposing between thesource of ultra-violet light and the substrate, or applying to thesubstrate a polymeric compound having a fluorene moiety(cyano(9H-fluoren-9-ylidene)acetic acid) attached to the polymerbackbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method of waterproofing a substrate surface byapplying thereto a polymeric compound having a fluorene moiety(cyano(9H-fluoren-9-ylidene)acetic acid) attached to the polymerbackbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method of protecting a photodegradable materialagainst photodegradation by applying thereto a polymeric compound havinga fluorene moiety (cyano(9H-fluoren-9-ylidene)acetic acid) attached tothe polymer backbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method of forming a UV-absorbing film on asubstrate surface by applying thereto film or coating containing apolymeric compound having a fluorene moiety(cyano(9H-fluoren-9-ylidene)acetic acid) attached to the polymerbackbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method for photostabilizing a sunscreencomposition including a photoactive compound by the addition of aphotostabilizing effective amount of a polymeric compound having afluorene moiety (cyano(9H-fluoren-9-ylidene)acetic acid) attached to thepolymer backbone.

Still another aspect of the compounds, compositions, and methodsdisclosed herein is to provide a polymeric compound having a crylenemoiety (2-cyano-3,3-diphenylacrylic acid) and a fluorene moiety(cyano(9H-fluoren-9-ylidene)acetic acid) attached to the polymerbackbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a sunscreen composition that includes a polymericcompound having a crylene moiety (2-cyano-3,3-diphenylacrylic acid) anda fluorene moiety (cyano(9H-fluoren-9-ylidene)acetic acid) attached tothe polymer backbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method of reducing or eliminating an amount ofultra-violet light that contacts a substrate by disposing between thesource of ultra-violet light and the substrate, or applying to thesubstrate a polymeric compound having a crylene moiety(2-cyano-3,3-diphenylacrylic acid) and a fluorene moiety(cyano(9H-fluoren-9-ylidene)acetic acid) attached to the polymerbackbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method of waterproofing a substrate surface byapplying thereto a polymeric compound having a crylene moiety(2-cyano-3,3-diphenylacrylic acid) and a fluorene moiety(cyano(9H-fluoren-9-ylidene)acetic acid) attached to the polymerbackbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method of protecting a photodegradable materialagainst photodegradation by applying thereto a polymeric compound havinga crylene moiety (2-cyano-3,3-diphenylacrylic acid) and a fluorenemoiety (cyano(9H-fluoren-9-ylidene)acetic acid) attached to the polymerbackbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method of forming a UV-absorbing film on asubstrate surface by applying thereto film or coating containing apolymeric compound having a crylene moiety (2-cyano-3,3-diphenylacrylicacid) and a fluorene moiety (cyano(9H-fluoren-9-ylidene)acetic acid)attached to the polymer backbone.

Another aspect of the compounds, compositions, and methods disclosedherein is to provide a method for photostabilizing a sunscreencomposition including a photoactive compound by the addition of aphotostabilizing effective amount of a polymeric compound having acrylene moiety (2-cyano-3,3-diphenylacrylic acid) and a fluorene moiety(cyano(9H-fluoren-9-ylidene)acetic acid) attached to the polymerbackbone.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Sunscreen compositions typically include one or more photoactivecompounds that can absorb UV radiation, and often sunscreen compositionsinclude a variety of photoactive compounds to absorb UV-radiation overthe entire UV range (UV-A and UB-B range). Compounds and compositionsthat include the photoactive moieties crylene(2-cyano-3,3-diphenylacrylic acid) and/or fluorene(cyano(9H-fluoren-9-ylidene)acetic acid), and methods of use of suchcompounds are described herein.

The general structure of a crylene moiety (2-cyano-3,3-diphenylacrylicacid) is shown below:

Optionally, each of the aromatic rings on the core crylene moiety can besubstituted with various functional groups. It has been found that theattachment of the crylene moiety, such as is found in the UV-absorberOctocrylene (shown below as A), may be attached to a polymer to convertthe polymer into a compound capable of absorbing and/or dissipating UVradiation, as well as to photostabilize another UV-absorbing compound.

An α-cyano-β,β-diphenylacrylate compound is known to quench (accept theexcited state energy) of an excited photoactive compound (see, e.g., thecommonly assigned U.S. patent application Ser. Nos. 10/241,388,10/361,223, and ______ (filed on Feb. 24, 2004). Without intending to belimited to any particular mechanism by which anα-cyano-β,β-diphenylacrylate compound is able to quench the excitedstate of photoactive compound, it is theorized that theα-cyano-β,β-diphenylacrylate compound accepts the excited state energyand dissipates the energy kinetically in the form of rapidisomerizations. This process is shown below:

wherein the α-cyano-β,β-diphenylacrylate compound (octocrylene shownabove as structure A), accepts the triplet excited state energy from aphotoactive compound and forms a diradical (shown above as structure A*)at the α and β positions of the acrylate, which converts the double bondinto a single bond and allows for the free rotation of the phenylgroups. This rotation occurs rapidly and efficiently to dissipate anyexcited state energy accepted by the α-cyano-β,β-diphenylacrylatecompound from the photoactive compound. In solution (e.g., a sunscreencomposition), a key limitation on the ability of a compound tophotostabilize another compound is the ability of the two compounds tocome into contact with one another.

The general structure of a fluorene moiety(cyano(9H-fluoren-9-ylidene)acetic acid) is shown below:

Optionally, each of the aromatic rings on the core crylene moiety can besubstituted with various functional groups. It has been found that afluorene moiety, such as is found in 2-ethylhexylcyano(9H-fluoren-9-ylidene) acetate), hereinafter referred to asoctofluorene, as shown below as structure B, may be attached to apolymer to convert the polymer into a compound capable of absorbingand/or dissipating UV radiation, as well as photostabilizing anotherUV-absorbing compound. Without intending to be limited to any particularmechanism by which such compounds are able to quench (accept the excitedstate energy) an excited photoactive compound, it is theorized that apolymer having a fluorene moiety attached thereto, for example a9-methylene-9H-fluorene, accepts the excited state energy from anotherUV-absorbing compound in an excited state and dissipates the energykinetically in the form of rapid isomerizations. An example of thisprocess is shown below:

wherein octofluorene (shown above as structure B) accepts the tripletexcited state energy and forms a diradical (shown above as structure B*)at the α and β positions of the acrylate, which converts the double bondinto a single bond and allows for free rotation about the single bond.This rotation occurs rapidly and efficiently to dissipate excited stateenergy accepted by a derivative of fluorene (a compound that includesthe fluorene moiety).

It has also been discovered that the novel UV-absorbing andphotostabilizing compounds disclosed in the commonly assigned U.S.patent application Ser Nos. 10/246,434, 10/458,286, 10/302,423, and10/385,833, the disclosures of which are hereby incorporated byreference, may be attached to a polymer molecule to provide other novelUV-absorbing and photostabilizing polymers. It has also been found thatthe polymer resulting from the attachment to the polymer backbone of thephotostabilizing compounds disclosed in the above-listed applicationswould create a polymer that can absorb UV-radiation and photostabilizeone or more other photoactive compounds in a UV-absorbing composition.

In accordance with another important “tether” embodiment of thecompounds, compositions, and methods disclosed herein, it has also beendiscovered that by attaching a tether to the crylene and/or fluorenemoieties and attaching the crylene and/or fluorene moieties to thepolymer backbone via the tether, the crylene and fluorene moieties arethereby spaced from the polymer backbone by attaching a tether (aspacer) so that there is less steric interference, to provide a moreeffective and efficient energy absorption and dissipation of the excitedstate energy via the aromatic ring(s) spinning about the tether(spacer). Suitable tether molecules include diols, diamino compounds, orany compound with two or more functional groups, wherein at least onefunctional group can be covalently attached to the carboxylic acid onthe crylene and/or fluorene moieties (e.g., an alcohol, amine,carboxylic acid, a sulfide), and another functional group that can becovalently bonded to the polymer backbone. Nonlimiting examples ofsuitable tethers include alkyl diols (e.g., neopentyl glycol), alkyldiamines (e.g., 1,5-diaminopentane), and alkyl amino alcohols(5-amino-1-pentanol). Another advantage to using a tether is thepotential to add additional hydrophobic or hydrophilic groups on thetether to influence the solubility properties of the resulting polymer.

Any polymers may be used in this “tether” embodiment so long as it iscapable of attachment of a tether molecule to its polymer backbone.Exemplary polymers that are useful include those having on its backbonea free alcohol, carboxylic acid, amine, and/or amide wherein thesefunctional groups can be covalently bonded to a crylene and/or fluorenemoiety, or a suitable tether. Copolymers of an α-olefin and maleicanhydride are particularly suitable for the attachment of a cryleneand/or fluorene moiety. Without intending to be limited to a particularmechanism of attachment, it is theorized that a crylene and/or afluorene moiety is covalently bonded to a copolymer of an α-olefin andmaleic anhydride is shown below for poly(octadecene-1-co-maleicanhydride):

wherein a and b are each in the range of 2 to 5000; c and d are each inthe range of 0 to 5000; and sum of c plus d is at least 2.

Copolymers that are suitable to be covalently bonded crylene and/orfluorene moiety (with or without a tether) include, but are not limitedto, Poly(alpha olefin-co-maleic anhydride), which can be preparedaccording the procedures set forth in U.S. Pat. Nos. 3,860,700,6,358,892, and U.S. Pat. Reissue No. 28,475, the disclosures of whichare hereby incorporated by reference. Examples of these resins includePoly(octadecene-1-co-maleic anhydride) resin (PA-18 available fromChevron Chemicals Co., San Francisco, Calif.), Poly(styrene-co-maleicanhydride) resin (SMA® resins, available from Atofina Chemicals Inc.Philadelphia, Pa.), Poly(ethylene-co-maleic anhydride) resin (EMA®,available from Monsanto, St. Louis, Mo.), Poly(isobutene-co-maleicanhydride) resin (ISOBAM® available form Kuraray Co. Ltd., Osaka,Japan), and Poly(methylvinylether-co-maleic anhydride) resin (Gantrez®An available from ISP, Wayne, N.J.). Alternatively, a mixture of alphaolefins may be used to form the maleic anhydride copolymer, and therebyprovide a versatile polymer with a number of different properties (e.g.,waterproofing and/or lubricating). Alternately mixtures of alpha olefinscan be used (e.g., Ketjenlube® resins available from Akzo Nobel Co.,Dobbs Ferry, N.Y.). Maleic anhydride polymers made with a mixture ofalpha olefins are described in U.S. Pat. Nos. 3,461,108, 3,560,455,3,560,456, 3,560,457, 3,580,893, 3,706,704, 3,729,450, and 3,729,451,the disclosures of which are hereby incorporated by reference.Preferably, the polymer used according to the invention is a Poly(alphaolefin-co-maleic anhydride) resin; more preferably, the polymer is aPoly(octadecene-1-co-maleic anhydride) resin.

Polymer backbone molecules of a particular polymer generally exists as amixture of polymer molecules of different chain lengths, wherein thepolymer is described as having a chain length that is an average of thechain lengths of the adjacent polymer molecules. Likewise, the molecularweight of a particular polymer can be determined in a number of ways,including a determination of the Weight Average Molecular Weight(M_(W)), which is the summation of the weights of each different sizedpolymer in a mixture multiplied by the mole fraction of that polymersize in the polymer mixture. Nonlimiting examples of methods ofcalculating a given polymer's Weight Average Molecular Weight includediffusion, sedimentation, flow birefringence, and light scattering.Preferably, a polymer disclosed herein has a Weight Average MolecularWeight is the range of about 20,000 to about 130,000 grams/mole, morepreferable in the range of about 30,000 to about 110,000 grams/mole.

Sunscreen compositions containing one or more photoactive compounds,such as a dibenzoylmethane derivative UV-A filter compound, and apolymer containing one or more crylene and/or fluorene moietiescovalently bonded to the polymer backbone are also described herein. Oneaspect of the sunscreen compositions described herein are methods ofphotostabilizing a sunscreen composition including a dibenzoylmethanederivative, such as 4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane(PARSOL® 1789), wherein one or more photoactive compounds present in asunscreen composition (e.g., avobenzone) are made more photostable bythe addition of a polymer containing one or more crylene and/or fluorenemoieties covalently bonded to the polymer backbone. Further disclosedherein are methods for filtering out ultra-violet light from human skinincluding the step of applying to the skin a cosmetically acceptablecomposition including a polymer containing one or more crylene and/orfluorene moieties covalently bonded to the polymer backbone. Alsodisclosed herein is a method of waterproofing a material by forming afilm on a surface of a material, wherein the film includes a polymercontaining one or more of crylene and/or fluorene moieties attached tothe polymer.

A photoactive compound can be considered stable when, for example, after30 MED irradiation the photoactive compound has retained at least about90% of its original absorbance at a wavelength, or over a range ofwavelengths of interest (e.g., the wavelength at which a photoactivecompound has a peak absorbance, such as 350-370 nm for avobenzone).Likewise, a sunscreen composition can include a plurality of photoactivecompounds and a sunscreen composition, as a whole, can be consideredstable when, for example, after 30 MED irradiation the sunscreencomposition has retained at least about 90% of its original absorbanceat one or more wavelengths of interest (e.g., at or near the peakabsorbance wavelength of the primary photoactive compound).

In commonly assigned U.S. patent application Ser. Nos. 10/241,388,10/361,223, and ______ (filed on Feb. 24, 2004), the disclosures ofwhich are hereby incorporated by reference, it was found that theaddition of an α-cyano-β,β-diphenylacrylate compound and a diester orpolyester of naphthalene dicarboxylic acid were able to stabilize aphotounstable UV-absorbing compound, e.g., a dibenzoylmethanederivative, such as PARSOL 1789, in a sunscreen composition. It hassurprisingly been found that sunscreen compositions containing acombination of (1) a polymer containing one or more crylene and/orfluorene moieties covalently bonded to the polymer backbone, and (2) adiester or polyester of naphthalene dicarboxylic acid can significantlyincrease the photostability of any photounstable component(s) presenttherein (e.g., a dibenzoylmethane derivative). Without intending to belimited to any particular mechanism of achieving this increase inphotostability, it is believed that a diester or polyester ofnaphthalene dicarboxylic acid stabilizes a dibenzoylmethane derivativeby accepting the triplet energy of the dibenzoylmethane derivative oncethe dibenzoylmethane derivative has reached an excited state as a resultof the absorption of ultra-violet light. Once a dibenzoylmethanederivative is excited, it is prone to degrade according to a number ofpathways; however, the degradation of the dibenzoylmethane derivativecan be substantially reduced or prevented by the use of a diester orpolyester of naphthalene dicarboxylic acid to quench (accept) thetriplet excited state energy present in an excited dibenzoylmethanemolecule. Thus, in one pathway of degradation, a dibenzoylmethanederivative is excited to its triplet state and the excited state tripletenergy is released in a bond breaking step, thereby preventing thedibenzoylmethane derivative from further accepting ultra-violetradiation. A diester or polyester of naphthalene dicarboxylic acid maystabilize a dibenzoylmethane derivative by accepting the triplet state(excited state) energy of the excited dibenzoylmethane derivative insuch a way as to convert the excited dibenzoylmethane derivative back toa ground state that is capable of reaccepting (or accepting additional)ultra-violet radiation (energy transfer).

For this process to work continuously, the diester or polyester ofnaphthalene dicarboxylic acid must transfer or convert the energy thatwas accepted from the excited dibenzoylmethane derivative. Withoutintending to be limited to a particular mechanism, it is believed thatwhen a diester or polyester of naphthalene dicarboxylic acid is excitedto its triplet state, it dissipates the triplet excited state energythrough vibrations (e.g., as heat), which in this group of molecules isa relatively slow mode of dissipating energy. It has been found, quitesurprisingly, that by the addition of a polymer containing one or morecrylene and/or fluorene moieties covalently bonded to the polymerbackbone, such a compound is able to accept triplet excited state energyfrom an excited diester or polyester of naphthalene dicarboxylic acid.Thus, according to one possible mechanism, the efficiency of thedissipation of the excited state energy in an excited diester orpolyester of naphthalene dicarboxylic acid is greatly improved by atransfer of energy from an excited diester or polyester of naphthalenedicarboxylic acid to the polymer containing one or more crylene and/orfluorene moieties.

Thus, preferably, a composition disclosed herein includes a diester orpolyester of naphthalene dicarboxylic acid selected from the groupconsisting of compounds of formulae (XIII) and (XIV), and combinationsthereof:

wherein R⁴³ and R⁴⁴ are the same or different and selected from thegroup consisting of C₁-C₂₂ alkyl groups, diols having the structureHO—R⁴¹—OH, and polyglycols having the structure HO—R⁴⁰—(—O—R⁴¹—)_(j)—OH;wherein each R⁴⁰ and R⁴¹ is the same or different and selected from thegroup consisting of C₁-C₆ straight or branched chain alkyl groups; andwherein h and j are each in a range of 1 to 100 and i is in a range of 0to 100.

The method of preparation of particularly useful diesters and polyestersof naphthalene dicarboxylic acid and the use of diesters and polyestersof naphthalene dicarboxylic acid in a sunscreen composition aredescribed in U.S. Pat. Nos. 5,993,789 and 6,284,916, the disclosures ofwhich are hereby incorporated herein by reference. Preferably, aUV-absorbing composition that includes a diester or polyester ofnaphthalene dicarboxylic acid includes a diester of formula (XIV)wherein R⁴³ and R⁴⁴ are 2-ethylhexane and p is 0. Preferably, theUV-absorbing compositions disclosed herein include a diester orpolyester of naphthalene dicarboxylic acid in a range of about 0.1% toabout 15% by weight of the total weight of the composition.

A sunscreen composition can be combined into a cosmetically acceptablecarrier, optionally including emollients, stabilizers, emulsifiers, suchas those known in the art, and combinations thereof. These additives canbe used in preparing an emulsion from an aqueous composition and amixture of a UV filter composition that includes one or more photoactivecompounds and a solvent or a solvent combination that includes one ormore organic solvents. When made, preferably the emulsion is anoil-in-water emulsion, wherein the oil phase is primarily formed from amixture of the filter system and solvent system.

A typical sunscreen composition includes one or more photoactivecompounds, wherein a photoactive compound acts to absorb UV radiationand thereby protect the substrate (e.g., human skin) from the harmfuleffects of UV radiation. The absorption process causes a photoactivecompound to reach an excited state, wherein the excited state ischaracterized by the presence of excited energy (e.g., singlet energy ortriplet energy), as compared to the ground state of the photoactivecompound. Once a photoactive compound reaches an excited state thereexists a number of pathways by which the excited photoactive compoundcan dissipate its excess energy (e.g., triplet energy), however, many ofthose pathways adversely affect the ability of the photoactive compoundto further absorb UV radiation.

It has surprisingly been found that the addition of polymers containingone or more crylene and/or fluorene moieties covalently bonded to thepolymer backbone increase the photostability of the sunscreencomposition. Without intending to be limited to any particular mechanismby which a such compounds are able to quench (accept the excited stateenergy) an excited photoactive compound, it is believed that, forexample the crylene and fluorene moieties accept the excited stateenergy and dissipates the energy kinetically in the form of rapidisomerizations. An example of this process is shown below wherein thePA-18 polymer (poly(octadecene-1-co-maleic anhydride)) having bothcrylene and fluorene moieties attached to the polymer backbone:

The polymer accepts the triplet excited state energy from a photoactivecompound and forms a diradical at the α and β positions of the acrylate,which converts the double bond into a single bond and allows for freerotation of the phenyl groups or fluorene group about the single bond.This rotation occurs rapidly and efficiently to dissipate excited stateenergy accepted by a derivative of fluorene.

Commonly-assigned U.S. Pat. Nos. 6,485,713 and 6,537,529, thedisclosures of which are hereby incorporated herein by reference,describe compositions and methods for increasing the photostability ofphotoactive compounds in a sunscreen composition, e.g., by the additionof polar solvents to the oil phase of a composition. It has been found,quite surprisingly, that by increasing the polarity of the oil phase ofa sunscreen composition including a polymer containing one or morecrylene and/or fluorene moieties covalently bonded to the polymerbackbone, the stability of the sunscreen composition is increased. Thus,in a sunscreen disclosed herein, preferably, one or more of a highlypolar solvent is present in the oil-phase of the composition.Preferably, a sufficient amount of a polar solvent is present in asunscreen composition to raise the dielectric constant of the oil-phaseof the composition to a dielectric constant of at least about 7,preferably at least about 8.

A photoactive compound is one that responds to light photoelectrically.In the compositions disclosed herein, a photoactive compound is one thatresponds to UV radiation photoelectrically. For example, photoactivecompounds that respond to UV radiation photoelectrically by rapidphotodegradation can benefit highly from the compositions and methodsdisclosed herein, even though the benefits of the compositions andmethods disclosed herein are not limited to such compounds.Photostability is a potential problem with all UV filters because theyare deliberately selected as UV-absorbing molecules. In otherapplications, a photoactive compound may be a pigment or a dye (e.g., ahydrophobic dye).

UV filters include compounds selected from the following categories(with specific examples) including: p-aminobenzoic acid, its salts andits derivatives (ethyl, isobutyl, glyceryl esters;p-dimethylaminobenzoic acid); anthranilates (o-aminobenzoates; methyl,menthyl, phenyl, benzyl, phenylethyl, linalyl, terpinyl, andcyclohexenyl esters); salicylates (octyl, amyl, phenyl, benzyl, menthyl(homosalate), glyceryl, and dipropyleneglycol esters); cinnamic acidderivatives (menthyl and benzyl esters, alpha-phenyl cinnamonitrile;butyl cinnamoyl pyruvate); dihydroxycinnamic acid derivatives(umbelliferone, methylumbelliferone, methylaceto-umbelliferone); camphorderivatives (3-benzylidene, 4-methylbenzylidene, polyacrylamidomethylbenzylidene, benzalkonium methosulfate, benzylidene camphor sulfonicacid, and terephthalylidene dicamphor sulfonic acid); trihydroxycinnamicacid derivatives (esculetin, methylesculetin, daphnetin, and theglucosides, esculin and daphnin); hydrocarbons (diphenylbutadiene,stilbene); dibenzalacetone; benzalacetophenone; naphtholsulfonates(sodium salts of 2-naphthol-3,6-disulfonic and of2-naphthol-6,8-disulfonic acids); dihydroxy-naphthoic acid and itssalts; o- and p-hydroxydiphenyldisulfonates; coumarin derivatives(7-hydroxy, 7-methyl, 3-phenyl); diazoles (2-acetyl-3-bromoindazole,phenyl benzoxazole, methyl naphthoxazole, various aryl benzothiazoles);quinine salts (bisulfate, sulfate, chloride, oleate, and tannate);quinoline derivatives (8-hydroxyquinoline salts, 2-phenylquinoline);hydroxy- or methoxy-substituted benzophenones; uric acid derivatives;vilouric acid derivatives; tannic acid and its derivatives;hydroquinone; and benzophenones (oxybenzone, sulisobenzone,dioxybenzone, benzoresorcinol, 2,2′,4,4′-tetrahydroxybenzophenone,2,2′-dihydroxy-4,4′-dimethoxybenzophenone, octabenzone,4-isopropyldibenzoylmethane, butylmethoxydibenzoylmethane, etocrylene,and 4-isopropyl-dibenzoylmethane).

Particularly useful are: 2-ethylhexyl p-methoxycinnamate, 4,4′-t-butylmethoxydibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyldimethylp-aminobenzoic acid, digalloyltrioleate,2,2-dihydroxy-4-methoxybenzophenone, ethyl4-[bis(hydroxypropyl)]aminobenzoate,2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexylsalicylate,glycerol p-aminobenzoate, 3,3,5-trimethylcyclohexylsalicylate,methylanthranilate, p-dimethylaminobenzoic acid or aminobenzoate,2-ethylhexyl p-dimethylaminobenzoate, 2-phenylbenzimidazole-5-sulfonicacid, 2-(p-dimethylaminophenyl-5-sulfoniobenzoxazoic acid, andcombinations thereof.

For a product marketed in the United States, preferredcosmetically-acceptable photoactive compounds and concentrations(reported as a percentage by weight of the total cosmetic sunscreencomposition) include: aminobenzoic acid (also called para-aminobenzoicacid and PABA; 15% or less), avobenzone (also called butyl methoxydibenzoylmethane; 3% or less), cinoxate (also called 2-ethoxyethylp-methoxycinnamate; 3% or less), dioxybenzone (also calledbenzophenone-8; 3% or less), homosalate (15% or less), menthylanthranilate (also called menthyl 2-aminobenzoate; 5% or less),octocrylene (also called 2-ethylhexyl-2-cyano-3,3 diphenylacrylate; 10%or less), octyl methoxycinnamate-(7.5% or less), octyl salicylate (alsocalled 2-ethylhexyl salicylate; 5% or less), oxybenzone (also calledbenzophenone-3; 6% or less), padimate O (also called octyl dimethylPABA; 8% or less), phenylbenzimidazole sulfonic acid (water soluble; 4%or less), sulisobenzone (also called benzophenone-4; 10% or less),titanium dioxide (25% or less), trolamine salicylate (also calledtriethanolamine salicylate; 12% or less), and zinc oxide (25% or less).

Other preferred cosmetically-acceptable photoactive compounds andpreferred concentrations (percent by weight of the total cosmeticsunscreen composition) include diethanolamine methoxycinnamate (10% orless), ethyl-[bis(hydroxypropyl)] aminobenzoate (5% or less), glycerylaminobenzoate (3% or less), 4-isopropyl dibenzoylmethane (5% or less),4-methylbenzylidene camphor (6% or less), terephthalylidene dicamphorsulfonic acid (10% or less), and sulisobenzone (also calledbenzophenone-4, 10% or less).

For a product marketed in the European Union, preferredcosmetically-acceptable photoactive compounds and preferredconcentrations (reported as a percentage by weight of the total cosmeticsunscreen composition) include: PABA (5% or less), camphor benzalkoniummethosulfate (6% or less), homosalate (10% or less), benzophenone-3 (10%or less), phenylbenzimidazole sulfonic acid (8% or less, expressed asacid), terephthalidene dicamphor sulfonic acid (10% or less, expressedas acid), butyl methoxydibenzoylmethane (5% or less), benzylidenecamphor sulfonic acid (6% or less, expressed as acid), octocrylene (10%or less, expressed as acid), polyacrylamidomethyl benzylidene camphor(6% or less), ethylhexyl methoxycinnamate (10% or less), PEG-25 PABA(10% or less), isoamyl p-methoxycinnamate (10% or less), ethylhexyltriazone (5% or less), drometrizole trielloxane (15% or less),diethylhexyl butamido triazone (10% or less), 4-methylbenzylidenecamphor (4% or less), 3-benzylidene camphor (2% or less), ethylhexylsalicylate (5% or less), ethylhexyl dimethyl PABA (8% or less),benzophenone-4 (5%, expressed as acid), methylene bis-benztriazolyltetramethylbutylphenol (10% or less), disodium phenyl dibenzimidazoletetrasulfonate (10% or less, expressed as acid), bis-ethylhexyloxyphenolmethoxyphenol triazine (10% or less), methylene bisbenzotriazolyltetramethylbutylphenol (10% or less, also called TINOSORB M), andbisethylhexyloxyphenol methoxyphenyl triazine.(10% or less, also calledTINOSORB S).

All of the above-described UV filters are commercially available. Forexample, suitable commercially-available organic UV filters areidentified by trade name and supplier in Table I below: TABLE I CTFAName Trade Name Supplier benzophenone-3 UVINULM-40 BASF Chemical Co.benzophenone-4 UVINUL MS-40 BASF Chemical Co. benzophenone-8SPECTRA-SORB American Cyanamid UV-24 DEA-methoxycinnamate BERNEL HYDROBernel Chemical ethyl dihydroxypropyl-PABA AMERSCREEN P Amerchol Corp.glyceryl PABA NIPA G.M.P.A. Nipa Labs. homosalate KEMESTER HMS HumkoChemical menthyl anthranilate SUNAROME UVA Felton Worldwide octocryleneUVINUL N-539 BASF Chemical Co. octyl dimethyl PABA AMERSCOL AmercholCorp. octyl methoxycinnamate PARSOL MCX Bernel Chemical PABA PABANational Starch 2-phenylbenzimidazole-5- EUSOLEX 6300 EM Industriessulphonic acid TEA salicylate SUNAROME W Felton Worldwide 2-(4- EUSOLEX6300 EM Industries methylbenzildene)-camphor benzophenone-1 UVINUL 400BASF Chemical Co. benzophenone-2 UVINUL D-50 BASF Chemical Co.benzophenone-6 UVINUL D-49 BASF Chemical Co. benzophenone-12 UVINUL 408BASF Chemical Co. 4-isopropyl dibenzoyl EUSOLEX 8020 EM Industriesmethane butyl methoxy dibenzoyl PARSOL 1789 Givaudan Corp. methaneetocrylene UVINUL N-35 BASF Chemical Co. methylene TINOSORB M Cibabisbenzotriazolyl Specialty Chemicals tetramethylbutylphenolbisethylhexyloxyphenol TINOSORB S Ciba methoxyphenyl Specialty Chemicalstriazine.

The term “alkyl” berein refers to straight- and branched-chainhydrocarbon groups, preferably containing one to thirty carbon atoms.Examples of alkyl groups are C₁-C₄ alkyl groups. As used herein thedesignation C_(x)-C_(y), wherein x and y are integers, denotes a grouphaving from x to y carbon atoms, e.g., a C₁-C₄ alkyl group is an alkylgroup having one to four carbon atoms. Nonlimiting examples of alkylgroups include, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl(2-methylpropyl), and t-butyl (1,l-dimethylethyl).

The term “cycloalkyl” as used herein refers to an aliphatic cyclichydrocarbon group, preferably containing three to eight carbon atoms.Nonlimiting examples of cycloalkyl groups include cyclopropyl,cyclobutyl, cyclopentyl, and cyclohexyl.

The terms “substituted alkyl” and “substituted cycloalkyl” as usedherein refer to an alkyl or cycloalkyl groups having one or moresubstituents. The substituents can include, but are not limited to,cycloalkyl, aryl, heteroaryl, heterocycloalkyl, substituted aryl,substituted heteroaryl, and substituted heterocycloalkyl. The preferredsubstituted alkyl groups have one to twenty carbon atoms, not includingcarbon atoms of the substituent group. Preferably, a substituted alkylgroup is mono- or di-substituted at one, two, or three carbon atoms. Thesubstituents can be bound to the same carbon or different carbon atoms.

The term “ester” as used herein refers to a group of the generalformula:

wherein R is an alkyl group, cycloalkyl group, substituted alkyl group,or a substituted cycloalkyl group.

The term “aryl” as used herein refers to monocyclic, fused bicyclic, andfused tricyclic carbocyclic aromatic ring systems including, but notlimited to, phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl,biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl.

The term “heteroaryl” as used herein refers to monocyclic, fusedbicyclic, and fused tricyclic aromatic ring systems, wherein one tofour-ring atoms are selected from the group consisting of oxygen,nitrogen, and sulfur, and the remaining ring atoms are carbon, said ringsystem being joined to the remainder of the molecule by any of the ringatoms. Nonlimiting examples of heteroaryl groups include, but are notlimited to, pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl,imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl,oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl,benzoxazolyl, benzimidazolyl, and benzothiazolyl.

The term “heterocycloalkyl” as used herein refers to an aliphatic,partially unsaturated or fully saturated, 3- to 1 4-membered ringsystem, including single rings of 3 to 8 atoms and bi- and tricyclicring systems. The heterocycloalkyl ring systems include one to fourheteroatoms independently selected from oxygen, nitrogen, and sulfur,wherein a nitrogen and sulfur heteroatom optionally can be oxidized anda nitrogen heteroatom optionally can be substituted. Representativeheterocycloalkyl groups include, but are not limited to, pyrrolidinyl,pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl,piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl,isothiazolidinyl, and tetrahydrofuryl.

The terms “substituted aryl,” “substituted heteroaryl,” and “substitutedheterocycloalkyl” as used herein refer to an aryl, heteroaryl, orheterocycloalkyl group substituted by a replacement of one, two, orthree of the hydrogen atoms thereon with a substitute selected from thegroup consisting of halo, OR, N(R)₂, C(═O)N(R)₂, CN, alkyl, substitutedalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl,cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, O(CH₂)₁₋₃N(R)₂, O(CH₂)₁₋₃CO₂H, and trifluoromethyl.

The term “amino” as used herein refers an —NH₂ or —NH— group, whereineach hydrogen in each formula can be replaced with an alkyl, cycloalkyl,aryl, heteroaryl, heterocycloalkyl, substituted alkyl, substitutedcycloalkyl, substituted aryl, substituted heteroaryl, or substitutedheterocycloalkyl group, i.e., N(R)₂. In the case of —NH₂, the hydrogenatoms also can be replaced with substituents taken together to form a 5-or 6-membered aromatic or non-aromatic ring, wherein one or two carbonsof the ring optionally are replaced with a heteroatom selected from thegroup consisting of sulfur, oxygen, and nitrogen. The ring alsooptionally can be substituted with an alkyl group. Examples of ringsformed by substituents taken together with the nitrogen atom includemorpholinyl, phenylpiperazinyl, imidazolyl, pyrrolidinyl,(N-methyl)piperazinyl, and piperidinyl.

The term “cyano” as used herein refers to a —C—N group, also designated—CN.

The terms “waterproof” and “waterproofing” as used herein refers to anyincrease in a material/surface's ability to repel water from permeatingthe material/surface. These terms are not intended to mean that amaterial/surface is completely impervious to water, rather, the terms“waterproof” and “waterproofing” are intended to be understood as makinga material/surface less water permeable relative to not having been“waterproofed” or having undergone “waterproofing.”

A sunscreen composition disclosed herein can include a variety ofphotoactive compounds, including one or more UV-A photoactive compoundsand one or more UV-B photoactive compounds. Preferably, a sunscreencomposition includes a photoactive compound selected from the groupconsisting of p-aminobenzoic acid and salts and derivatives thereof;anthranilate and derivatives thereof; dibenzoylmethane and derivativesthereof; salicylate and derivatives thereof; cinnamic acid andderivatives thereof; dihydroxycinnamic acid and derivatives thereof;camphor and salts and derivatives thereof; trihydroxycinnamic acid andderivatives thereof; dibenzalacetone naphtholsulfonate and salts andderivatives thereof; benzalacetophenone naphtholsulfonate and salts andderivatives thereof; dihydroxy-naphthoic acid and salts thereof;o-hydroxydiphenyldisulfonate and salts and derivatives thereof;p-hydroxydiphenyldisulfonate and salts and derivatives thereof; coumarinand derivatives thereof; diazole derivatives; quinine derivatives andsalts thereof; quinoline derivatives; hydroxy-substituted benzophenonederivatives; methoxy-substituted benzophenone derivatives; uric acidderivatives;: vilouric acid derivatives; tannic acid and derivativesthereof; hydroquinone; benzophenone derivatives; 1,3,5-triazinederivatives, phenyldibenzimidazole tetrasulfonate and salts andderivatives thereof; terephthalylidene dicamphor sulfonic acid and saltsand derivatives thereof; methylene bis-benzotriazolyltetramethylbutylphenol and salts and derivatives thereof;bis-ethylhexyloxyphenol methoxyphenyl triazine and salts and derivativesthereof; diethylamino hydroxybenzoyl hexyl benzoate and salts andderivatives thereof; and combinations of the foregoing.

UV-A radiation (about 320 nm to about 400 nm), is recognized ascontributing to causing damage, to skin particularly to verylightly-colored or sensitive skin. A sunscreen composition disclosedherein preferably includes a UV-A photoactive compound. Preferably, asunscreen composition disclosed herein includes a dibenzoylmethanederivative UV-A photoactive compound. Preferred dibenzoylmethanederivatives include, 2-methyldibenzoylmethane; 4-methyldibenzoylmethane;4-isopropyldibenzoylmethane; 4-tert-butyldibenzoylmethane;2,4-dimethyldibenzoylmethane; 2,5-dimethyldibenzoylmethane;4,4′-diisopropyldibenzoylmethane; 4,4′-dimethoxydibenzoylmethane;4-tert-butyl-4′-methoxydibenzoylmethane;2-methyl-5-isopropyl-4′-methoxydibenzoylmethane;2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane;2,4-dimethyl-4′-methoxydibenzoylmethane;2,6-dimethyl-4-tert-butyl-4′-methoxydibenzoylmethane, and combinationsthereof.

A preferred combination of photoactive compounds in a sunscreencomposition includes a UV-A and a UV-B photoactive compound. However,when 2-ethylhexyl-p-methoxycinnamate is included in a mixture with adibenzoylmethane derivative, the dibenzoylmethane derivative can becomeparticularly unstable. Without intending to be limited to any particularmechanism, it is believed that the cinnamate ester reacts with anexcited-state dibenzoylmethane derivative in a bimolecular pathway thatrenders both the dibenzoylmethane derivative and the cinnamate esterincapable of absorbing UV radiation. It has been found, quitesurprisingly, that the use of a polymer containing one or more cryleneand/or fluorene moieties covalently bonded to the polymer backboneincreases the stability of a sunscreen composition that includes2-ethylhexyl-p-methoxycinnamate and a dibenzoylmethane derivative. Thus,one embodiment of a sunscreen composition includes2-ethylhexyl-p-methoxycinnamate, a dibenzoylmethane derivative, and apolymer containing one or more crylene and/or fluorene moietiescovalently bonded to the polymer backbone.

One embodiment of a polymer compound disclosed herein is a compound offormula (I):

wherein R¹, R², R³, R^(4,) R⁵, and R⁶ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, e, g, f, and h are eachin the range of 0 to 4, m and n are each in the range of 0 to 5000, andthe sum of m plus n is at least 1. Preferably, R¹ and R² are selectedfrom the group consisting of C₁-C₃₀ alkyl groups. More preferably, R¹ isa C₁₆ straight chain alkyl group, and R² is a 2,2-dimethylpropyl group.

Another embodiment of a polymer compound disclosed herein is a compoundof formula (II):

wherein R⁷, R⁸, R⁹, and R¹⁰ are the same or different and selected fromthe group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl,heterocycloalkyl, substituted aryl, substituted heteroaryl, substitutedheterocycloalkyl, cyano, and amino, i, j, k, and l are each in the rangeof 0 to 4, o and p are each in the range of 0 to 5000, and the sum of oplus p is at least 1. Compound of formula (II) are also referred toherein as Octadecene/Crylene maleate copolymer.

Another embodiment of a polymer compound disclosed herein is the productof the reaction between the polymer of formula (III) and a compoundselected from the group consisting of compounds of formulae (IV), (V),and combinations thereof:

wherein R¹¹, R¹², R¹³, R¹⁴, and R³⁹ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, m, n, o, and p are eachin the range of 0 to 4, and q is in the range of 2 to 5000. Preferably,R³⁹ is selected from the group consisting of C₁-C₃₀ alkyl groups. Morepreferably, R³⁹ is a C₁₆ straight chain alkyl group.

Compounds of formula (I), quite surprisingly, are able to increase thestability of a photoactive compound in a sunscreen composition.Accordingly, another embodiment is a sunscreen composition sunscreencomposition, including a mixture of a photoactive compound, and acompound of formula (I):

wherein R¹, R², R³, R^(4,) R⁵, and R⁶ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, e, g, f, and h are eachin the range of 0 to 4, m and n are each in the range of 0 to 5000, andthe sum of m plus n is at least 1. Preferably, R¹ and R² are selectedfrom the group consisting of C₁-C₃₀ alkyl groups. More preferably, R¹ isa C₁₆ straight chain alkyl group, and R² is a 2,2-dimethylpropyl group.Preferably, a compound of formula (I) is present in a sunscreencomposition in a range of about 0.01% to about 30% by weight of thetotal weight of the composition, more preferably in a range of about0.1% to about 10%.

Compounds of formula (I), quite surprisingly, are able to absorbUV-radiation and to increase the photostability of a photoactivecompound in a sunscreen composition, the compounds of formula (I) aretherefore able to be used to protect skin from the harmful effects ofUV-radiation. FIG. 1 shows the absorbance spectra from 280 nm to 400 nmfor a sunscreen composition wherein Octadecene/Crylene maleate copolymer(a compound of formula (I) wherein R¹ is a C₁₆ straight chain alkylgroup, R² is a 2,2-dimethylpropyl group, and there is no substitution ofthe aromatic rings of the crylene moieties) is present as the onlyUV-absorbing compound. FIG. 2 is a graph of the absorbance spectra from280 nm to 400 nm for the sunscreen compositions shown in Table III, andthe composition shown in Table II, wherein Octadecene/Crylene maleatecopolymer is included as the only UV-absorbing compound. FIG. 2 confirmsthat Octadecene/Crylene maleate copolymer absorbs UV-radiationindependent of other UV-absorbing agents that may be present in asunscreen composition. Accordingly, another embodiment is a method ofprotecting human skin from ultraviolet radiation, including topicallyapplying to the skin, in a cosmetically acceptable carrier, a compoundof formula (I):

wherein R¹, R², R³, R^(4,) R⁵, and R⁶ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, e, g, f, and h are eachin the range of 0 to 4, m and n are each in the range of 0 to 5000, andthe sum of m plus n is at least 1. Preferably, R¹ and R² are selectedfrom the group consisting of C₁-C₃₀ alkyl groups. More preferably, R¹ isa C₁₆ straight chain alkyl group, and R² is a 2,2-dimethylpropyl group.Preferably, a compound of formula (I) is present in a sunscreencomposition in a range of about 0.01% to about 30% by weight of thetotal weight of the composition, more preferably in a range of about0.1% to about 10%.

It has been found that a polymer compound of formula (I) may be used towaterproof a surface, and thereby, make the surface less waterpermeable. This aspect of a compound of formula (I) may be used in avariety of applications, including a sunscreen composition. A compoundof formula (I) may be added to a sunscreen composition to help preventthe loss of the composition that may accompany the immersion in water ofthe object (e.g., human skin) that has been applied with thecomposition. Accordingly, another embodiment is a method ofwaterproofing a surface, including applying a compound of formula (I) toa selected area of the surface:

wherein R¹, R², R³, R^(4,) R⁵, and R⁶ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, e, g, f, and h are eachin the range of 0 to 4, m and n are each in the range of 0 to 5000, andthe sum of m plus n is at least 1. Preferably, R¹ and R² are selectedfrom the group consisting of C₁-C₃₀ alkyl groups. More preferably, R¹ isa C₁₆ straight chain alkyl group, and R² is a 2,2-dimethylpropyl group.

It has also been found that a polymer compound of formula (I) may beused to form a film on a surface, and when added to a composition, acompound of formula (I) may provide film-forming properties to thecomposition. Accordingly, another embodiment is a method for forming afilm over at least part of a surface, including spreading a compound offormula (I) on the part of the surface:

wherein R¹, R², R³, R^(4,) R⁵, and R⁶ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, e, g, f, and h are eachin the range of 0 to 4, m and n are each in the range of 0 to 5000, andthe sum of m plus n is at least 1. Preferably, R¹ and R² are selectedfrom the group consisting of C₁-C₃₀ alkyl groups. More preferably, R¹ isa C₁₆ straight chain alkyl group, and R² is a 2,2-dimethylpropyl group.

Likewise, a compound of formula (I), quite surprisingly, is able toincrease the photostability of a dibenzoylmethane derivative. Withoutintending to be limited to a particular mechanism, it is believed that acompound selected from the group consisting of compounds of formula (I)are able to photostabilize a dibenzoylmethane derivative by acceptingthe triplet excited energy from an excited dibenzoylmethane derivative.Thus, another embodiment of the compounds, compositions, and methodsdisclosed herein is to provide a method of photostabilizing adibenzoylmethane derivative, the method including the step of, adding tothe dibenzoylmethane derivative a photostabilizing amount of a compoundof formula (I):

wherein R¹, R², R³, R^(4,) R⁵, and R⁶ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, e, g, f, and h are eachin the range of 0 to 4, m and n are each in the range of 0 to 5000, andthe sum of m plus n is at least 1. Preferably, R¹ and R² are selectedfrom the group consisting of C₁C₋₃₀ alkyl groups. More preferably, R¹ isa C₁₆ straight chain alkyl group, and R² is a 2,2-dimethylpropyl group.

Yet another embodiment of a polymer compound disclosed herein is acompound of formula (VI):

wherein R³, R⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, s, t, u, and v are eachin the range of 0 to 4, q and r are each in the range of 0 to 5000, andthe sum of q plus r is at least 1. Preferably, R³ and R⁴ are selectedfrom the group consisting of C₁-C₃₀ alkyl groups. More preferably, R³ isa C₁₆ straight chain alkyl group, and R⁴ is a 2,2-dimethylpropyl group.

Another embodiment of a polymer compound disclosed herein is a compoundof formula (VII):

wherein R¹⁹, R²⁰, R²¹, and R²² are the same or different and selectedfrom the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl,C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl,heterocycloalkyl, substituted aryl, substituted heteroaryl, substitutedheterocycloalkyl, cyano, and amino, w, x, y, and z are each in the rangeof 0 to 4, s and t are each in the range of 0 to 5000, and the sum of splus t is at least 1.

Compounds of formula (VI), quite surprisingly, are able to increase thestability of a photoactive compound in a sunscreen composition.Accordingly, another embodiment is a sunscreen composition sunscreencomposition, including a mixture of a photoactive compound, and acompound of formula (VI):

wherein R³, R⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, s, t, u, and v are eachin the range of 0 to 4, q and r are each in the range of 0 to 5000, andthe sum of q plus r is at least 1. Preferably, R³ and R⁴ are selectedfrom the group consisting of C₁-C₃ alkyl groups. More preferably, R³ isa C₁₆ straight chain alkyl group, and R⁴ is a 2,2-dimethylpropyl group.Preferably, a compound of formula (VI) is present in a sunscreencomposition in a range of about 0.01% to about 30% by weight of thetotal weight of the composition, more preferably in a range of about0.1% to about 10%.

Compounds of formula (VI), quite surprisingly, are able to absorbUV-radiation and to increase the photostability of a photoactivecompound in a sunscreen composition, the compounds of formula (VI) aretherefore able to be used to protect skin from the harmful effects ofUV-radiation. Accordingly, another embodiment is a method of protectinghuman skin from ultraviolet radiation, including topically applying tothe skin, in a cosmetically acceptable carrier, a compound of formula(VI):

wherein R³, R⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl C₁-C₃₀ substitutedalkyl C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, s, t, u, and v are eachin the range of 0 to 4, q and r are each in the range of 0 to 5000, andthe sum of q plus r is at least 1. Preferably, R³ and R⁴ are selectedfrom the group consisting of C₁-C₃₀ alkyl groups. More preferably, R³ isa C₁₆ straight chain alkyl group, and R⁴ is a 2,2-dimethylpropyl group.Preferably, a compound of formula (VI) is present in a sunscreencomposition in a range of about 0.01% to about 30% by weight of thetotal weight of the composition, more preferably in a range of about0.1% to about 10%.

It has been found that a polymer compound of formula (VI) may be used towaterproof a surface, and thereby, make the surface less waterpermeable. This aspect of a compound of formula (VI) may be used in avariety of applications, including a sunscreen composition. A compoundof formula (VI) may be added to a sunscreen composition to help preventthe loss of the composition that may accompany the immersion in water ofthe object (e.g., human skin) that has been applied with thecomposition. Accordingly, another embodiment is a method ofwaterproofing a surface, including applying a compound of formula (VI)to a selected area of the surface:

wherein R³, R⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, s, t, u, and v are eachin the range of 0 to 4, q and r are each in the range of 0 to 5000, andthe sum of q plus r is at least 1. Preferably, R³ and R⁴are selectedfrom the group consisting of C₁-C₃₀ alkyl groups. More preferably, R³ isa C₁₆ straight chain alkyl group, and R⁴ is a 2,2-dimethylpropyl group.

It has also been found that a polymer compound of formula (VI) may beused to form a film on a surface, and when added to a composition, acompound of formula (VI) may provide film-forming properties to thecomposition. Accordingly, another embodiment is a method for forming afilm over at least part of a surface, including spreading a compound offormula (VI) on the part of the surface:

wherein R³, R⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, s, t, u, and v are eachin the range of 0 to 4, q and r are each in the range of 0 to 5000, andthe sum of q plus r is at least 1. Preferably, R³ and R⁴ are selectedfrom the group consisting of C₁-C₃₀alkyl groups. More preferably, R³ isa C₁₆ straight chain alkyl group, and R⁴ is a 2,2-dimethylpropyl group.

Likewise, a compound of formulae (VI), quite surprisingly, is able toincrease the photostability of a dibenzoylmethane derivative. Withoutintending to be limited to a particular mechanism, it is believed that acompound selected from the group consisting of compounds of formula (VI)are able to photostabilize a dibenzoylmethane derivative by acceptingthe triplet excited energy from an excited dibenzoylmethane derivative.Thus, another embodiment of the compounds, compositions, and methodsdisclosed herein is a method of photostabilizing a dibenzoylmethanederivative, the method including the step of, adding to thedibenzoylmethane derivative a photostabilizing amount of a compound offormula (VI):

wherein R³, R⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, s, t, u, and v are eachin the range of 0 to 4, q and r are each in the range of 0 to 5000, andthe sum of q plus r is at least 1. Preferably, R³ and R⁴ are selectedfrom the group consisting of C₁-C₃₀ alkyl groups: More preferably, R³ isa C₁₆ straight chain alkyl group, and R⁴ is a 2,2-dimethylpropyl group.

Yet another embodiment of a polymer compound disclosed herein is acompound of formula (IX):

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵,R³⁶, R³⁷, and R³⁸ are the same or different and selected from the groupconsisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈ cycloalkyl,C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl, heterocycloalkyl,substituted aryl, substituted heteroaryl, substituted heterocycloalkyl,cyano, and amino, e, f, h, i, j, k, l, and m are each in the range of 0to 4, a, b, c, and d are each in the range of 0 to 5000, and the sum ofa, b, c, and d is at least 1. Preferably, R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸,R²⁹, and R³⁰ are selected from the group consisting of C₁-C₃₀ alkylgroups. More preferably, R²³, R²⁴, R²⁵⁴, R²⁶ are C₁₆ straight chainalkyl groups, and R²⁷, R²⁸, R²⁹, and R³⁰ are 2,2-dimethylpropyl groups.

Another embodiment of a polymer compound disclosed herein is a compoundof formula (X):

wherein R³⁹, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ are the same ordifferent and selected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀substituted alkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl,ester, aryl, heteroaryl, heterocycloalkyl, substituted aryl, substitutedheteroaryl, substituted heterocycloalkyl, cyano, and amino, r, s, t, u,v, w, x, and y are each in the range of 0 to 4, n, o, p, and q are eachin the range of 0 to 5000, and the sum of n, o, p, and q is at least 1.

Compounds of formula (IX), quite surprisingly, are able to increase thestability of a photoactive compound in a sunscreen composition.Accordingly, another embodiment is a sunscreen composition sunscreencomposition, including a mixture of a photoactive compound, and acompound of formula (IX):

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵,R³⁶, R³⁷, and R³⁸ are the same or different and selected from the groupconsisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈ cycloalkyl,C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl, heterocycloalkyl,substituted aryl, substituted heteroaryl, substituted heterocycloalkyl,cyano, and amino, e, f, h, i, j, k, l, and m are each in the range of 0to 4, a, b, c, and d are each in the range of 0 to 5000, and the sum ofa, b, c, and d is at least 1. Preferably, R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸,R²⁹, and R³⁰ are selected from the group consisting of C₁-C₃₀ alkylgroups. More preferably, R²³, R²⁴, R²⁵, R²⁶ are C₁₆ straight chain alkylgroups, and R²⁷, R²⁸, R²⁹, and R³⁰ are 2,2-dimethylpropyl groups.Preferably, a compound of formula (IX) is present in a sunscreencomposition in a range of about 0.01% to about 30% by weight of thetotal weight of the composition, more preferably in a range of about0.1% to about 10%.

Compounds of formula (IX), quite surprisingly, are able to absorbUV-radiation and to increase the photostability of a photoactivecompound in a sunscreen composition, the compounds of formula (IX) aretherefore able to be used to protect skin from the harmful effects ofUV-radiation. Accordingly, another embodiment is a method of protectinghuman skin from ultraviolet radiation, including topically applying tothe skin, in a cosmetically acceptable carrier, a compound of formula(IX):

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵,R³⁶, R³⁷, and R³⁸ are the same or different and selected from the groupconsisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈ cycloalkyl,C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl, heterocycloalkyl,substituted aryl, substituted heteroaryl, substituted heterocycloalkyl,cyano, and amino, e, f, h, i, j, k, l, and m are each in the range of 0to 4, a, b, c, and d are each in the range of 0 to 5000, and the sum ofa, b, c, and d is at least 1. Preferably, R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸,R²⁹, and R³⁰ are selected from the group consisting of C₁-C₃₀ alkylgroups. More preferably, R²³, R²⁴, R²⁵, R²⁶ are C₁₆ straight chain alkylgroups, and R²⁷, R²⁸, R²⁹, and R³⁰ are 2,2-dimethylpropyl groups.Preferably, a compound of formula (IX) is present in a sunscreencomposition in a range of about 0.01% to about 30% by weight of thetotal weight of the composition, more preferably in a range of about0.1% to about 10%.

It has been found that a polymer compound of formula (IX) may be used towaterproof a surface, and thereby, make the surface less waterpermeable. This aspect of a compound of formula (IX) may be used in avariety of applications, including a sunscreen composition. A compoundof formula (IX) may be added to a sunscreen composition to help preventthe loss of the composition that may accompany the immersion in water ofthe object (e.g., human skin) that has been applied with thecomposition. Accordingly, another embodiment is a method ofwaterproofing a surface, including applying a compound of formula (IX)to a selected area of the surface:

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³², R³³, R³⁴, R³⁵, R³⁶,R³⁷, and R³⁸ are the same or different and selected from the groupconsisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈ cycloalkyl,C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl, heterocycloalkyl,substituted aryl, substituted heteroaryl, substituted heterocycloalkyl,cyano, and amino, e, f, h, i, j, k, l, and m are each in the range of 0to 4, a, b, c, and d are each in the range of 0 to 5000, and the sum ofa, b, c, and d is at least 1. Preferably R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸,R²⁹, and R³⁰ are selected from the group consisting of C₁-C₃₀ alkylgroups. More preferably, R²³, R²⁴, R²⁵, R²⁶ are C₁₆ straight chain alkylgroups, and R²⁷, R²⁸, R²⁹, and R³⁰ are 2,2-dimethylpropyl groups.

It has also been found that a polymer compound of formula (IX) may beused to form a film on a surface, and when added to a composition, acompound of formula (IX) may provide film-forming properties to thecomposition. Accordingly, another embodiment is a method for forming afilm over at least part of a surface, including spreading a compound offormula (IX) on the part of the surface:

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵,R³⁶, R³⁷, and R³⁸ are the same or different and selected from the groupconsisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈ cycloalkyl,C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl, heterocycloalkyl,substituted aryl, substituted heteroaryl, substituted heterocycloalkyl,cyano, and amino, e, f, h, i, j, k, l, and m are each in the range of 0to 4, a, b, c, and d are each in the range of 0 to 5000, and the sum ofa, b, c, and d is at least 1. Preferably, R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸,R²⁹, and R³⁰ are selected from the group consisting of C₁-C₃₀ alkylgroups. More preferably, R²³, R²⁴, R²⁵, R²⁶ are C₁₆ straight chain alkylgroups, and R²⁷, R²⁸, R²⁹, and R³⁰ are 2,2-dimethylpropyl groups.

Likewise, a compound of formulae (IX), quite surprisingly, is able toincrease the photostability of a dibenzoylmethane derivative. Withoutintending to be limited to a particular mechanism, it is believed that acompound selected from the group consisting of compounds of formula (IX)are able to photostabilize a dibenzoylmethane derivative by acceptingthe triplet excited energy from an excited dibenzoylmethane derivative.Thus, another embodiment of the compounds, compositions, and methodsdisclosed herein is a method of photostabilizing a dibenzoylmethanederivative, the method including the step of, adding to thedibenzoylmethane derivative a photostabilizing amount of a compound offormula (IX):

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁵, R³⁶,R³⁷, and R³⁸ are the same or different and selected from the groupconsisting of C₁-C₃₀ alkyl, C₁-C_(substituted alkyl, C) ₃-C₈ cycloalkyl,C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl, heterocycloalkyl,substituted aryl, substituted heteroaryl, substituted heterocycloalkyl,cyano, and amino, e, f, h, i, j, k, l, and m are each in the range of 0to 4, a, b, c, and d are each in the range of 0 to 5000, and the sum ofa, b, c, and d is at least 1. Preferably, R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸,R²⁹, and R³⁰ are selected from the group consisting of C₁-C₃₀ alkylgroups. More preferably, R²³, R²⁴, R²⁵, R²⁶ are C₁₆ straight chain alkylgroups, and R²⁷, R²⁸, R²⁹, and R³⁰ are 2,2-dimethylpropyl groups.

EXAMPLES

The following examples are provided to illustrate the compounds,compositions, and methods disclosed herein but are not intended to limitthe scope of the compounds, compositions, and methods disclosed herein.

Example 1

The following is a preparation for a polymer compound containing crylenemoieties attached to the polymer backbone, whereinPoly(octadecene-1-co-maleic anhydride) resin (PA-18 available fromChevron Chemicals Co., San Francisco, Calif.) served as a polymerstarting material, and2,2-dimethyl-3-hydroxypropyl-2-cyano-3,3-diphenylpropenoate served asthe crylene moiety with a tether of neopentyl glycol. The PA-18Polyanhydride Resin (300 g) and2,2-dimethyl-3-hydroxypropyl-2-cyano-3,3-diphenylpropenoate (258 g) wereplaced in 2L 3-neck round-bottom flask and 800 ml of toluene was added.The reaction mixture was then heated and refluxed for two hours untilreaction was completed (as determined by GPC). The product in solutionwas placed in evaporation vessels to remove the solvent. The finalproduct was then dried and ground to give off-white powder (510 g, 91%yield).

Example 2

A composition which included only the Octadecene/Crylene maleatecopolymer as the only UV-Absorbing compound by mixing the ingredientsshown in Table II below: TABLE II Weight Phase Ingredient Percent ACaprylic/capric triglycerides 8.00% Polyisobutene 3.00% Phenylethylbenzoate 1.00% Diethylhexyl malate 2.00% B Octadecene/Crylene maleatecopolymer 2.00% C Stearyl alcohol 1.00% Steareth-21 0.22% Steareth-20.28% Polyglyceryl-3 methyl glucose distearate 3.00% D Dimethicone (100cSt) 0.40% E Water 72.56% Disodium EDTA 0.05% Carbomer 0.20% F Sorbitol(70%) 4.29% Phenoxyethanol, Methylparaben, Ethylparaben, 1.00%Propylparaben, and Isobutylparaben Triethanolamine 1.00%

An oil-in-water emulsion was created, wherein the aqueous phase includeda mixture of the ingredients in Phase E, and the oil phase included amixture of the ingredients of Phases A, B, C, and D. The emulsion wasprepared by combining the ingredients of Phase A, and adding thismixture of ingredients to a vessel, and heating the vessel to about 90°C. The ingredients from Phases B, C, and D were then added to the heatedvessel with stirring until the mixture became clear and homogeneous. Inanother vessel, the ingredients of Phase E were added in the order shownin Table II, with continuous stirring. The vessel containing theingredients of Phase E was then heated to about 80° C. Withhomogenization, the contents of the vessel containing the oil phase (amixture of the ingredients of Phases A, B, C, and D) were added to thevessel containing the water phase (a mixture of the ingredients of PhaseE). The resulting mixture was homogenized for three minutes, and thenthe vessel was remove from heat source and allowed to cool. When thetemperature of the mixture fell below 40° C., the ingredients of Phase Fwere added. The mixture was stirred until a smooth cream was formed. Theresulting cream was then packaged to avoid the inadvertentphotodegradation of the UV-absorbing compounds in the composition.

FIG. 1 is a graph of the percent absorbance of the sunscreen compositionlisted in Table II. As shown in FIG. 1, the Octadecene/Crylene maleatecopolymer absorbs over the entire UV-spectrum, but achieves its maximumabsorbance in the range of about 290-330 nm.

Example 3

Two sunscreen compositions were prepared by mixing the ingredients shownin Table III below: TABLE III Sunscreen w/0% Polymer Sunscreen w/2%Phase Ingredient (wt. %) Polymer (wt. %) A Octyl salicylate 5.00% 5.00%Homosalate 7.50% 7.50% Diethylhexyl 2,6-naphthalate 2.50% 2.50%Octocrylene 2.50% 2.50% Dimethyl capramide 1.00% 1.00% Diethylhexylmalate 2.01% 2.01% B Avobenzone 3.00% 3.00% Benzophenone-3 0.49% 0.49% COctyldodecanol 2.00% Octadecene/Crylene maleate 2.00% copolymer DStearyl alcohol 1.00% 1.00% Steareth 21 0.29% 0.29% Steareth 2 0.21%0.21% Polyglyceryl-3 methyl glucose 3.00% 3.00% distearate E Water64.16%  63.16%  Disodium EDTA 0.05% 0.05% Carbomer 0.20% 0.20% Sorbitol(70%) 4.29% 4.29% Phenoxyethanol, Methylparaben, 0.60% 0.60%Ethylparaben, Propylparaben, and Isobutylparaben F Triethanolamine  0.2% 1.2%

Oil-in-water emulsions were created, wherein the aqueous phase includeda mixture of the ingredients in Phase E, and the oil phase included amixture of the ingredients of Phases A, B, C, and D. The emulsions wereprepared by combining the ingredients of Phase A, and adding thismixture of ingredients to a vessel, and heating the vessel to about 90°C. The ingredients from Phases B, C, and D were then added to the heatedvessel with stirring until the mixture became clear and homogeneous. Inanother vessel, the ingredients of Phase E were added in the order shownin Table III, with continuous stirring. The vessel containing theingredients of Phase E was then heated to about 80° C. Withhomogenization, the contents of the vessel containing the oil phase (amixture of the ingredients of Phases A, B, C, and D) to the vesselcontaining the water phase (a mixture of the ingredients of Phase E).The resulting mixture was homogenized for three minutes, and then thevessel was remove from heat source and allowed to cool. When temperatureof the mixture fell below 40° C., the ingredient of Phase F(triethanolamine) was added. The mixture was stirred until a smoothcream was formed. The resulting creams were packaged to avoid theinadvertent photodegradation of the UV-absorbing compounds, and thecreams were then used to test the photostability of the compositions.

The resulting sunscreens were tested for photostability by measuringabsorbance on a Labsphere UV-1000S Ultraviolet Transmittance Analyzer(software version 1.27) before and after irradiation with a Solar LightCompany model 16S solar simulator (equipped with a UG11 filter to blockradiation greater than 400 nm, WG320 filter that transmits UV-radiationgreater than 290 nm), and a removable WG335 filter that transmitsUV-radiation greater than 320 nm). Output was monitored by a PMA 2105UV-B DCS Detector (biologically weighted) or a PMA 2114 UV-A Detectorand controlled by a PMA 2100 Automatic Dose Controller (available fromSolar Light Co.).

To test stability, a synthetic skin substrate was used for testing thesunscreen compositions (VITRO-SKIN substrate (Lot No. 3059) by IMS, Inc.of Milford, Conn.). To prepare the substrate, a 300 g solution of 18 wt.% glycerin and 82 wt. % deionized water was added to a hydrating chamber(IMS), and a sheet of VITRO-SKIN was placed in the hydrating chamber andleft overnight (approx. 16 hours). Several 6.5 cm squares were cut fromthe hydrated VITRO-SKIN and used for absorbance measurements.

To prepare slides for testing, a minimum 100 μl of sunscreen compositionis drawn or placed into a pipet tip (Justor 1100DG, set to dispense 100μl). Using steady, even pressure on the pipette plunger, the testsubstance was applied to VITRO-SKIN square in a pattern of at least 50small dots arranged to cover a 6 cm center of a square. The VITRO-SKINsquare was then placed on a foam block, and the test material was spreadby finger (covered with a latex glove or finger cot), first in acircular motion, then by a side-to-side motion during which theVITRO-SKIN is deformed by the pressure. The square was then mounted in aslide holder (60 mm×60 mm glassless slide mounts with metal masks byGepe Management AG, Zug, Switzerland) and allowed to dry for 30-60minutes.

It has been found that to avoid certain errors of an as yet unknowncause, it is advantageous to pre-expose the tested spot on the slide to2 MED, and then zero the detector to treat the pre-exposed spot as a 0MED reading. Thus, using the PMA 2105 UV-B detector, a pre-exposure of 2MED was made. Immediately following the pre-exposure, the slide is takento the UV Transmittance Analyzer and the irradiated spot is scanned. Theoriginal scan is deleted, and the new scan is saved as the baseline (“0MED”) scan.

To test stability of a slide in the UV-B range, the PMA 2105 was used,and the slide was positioned on the UV transmittance analyzer usingregistration marks, and a scan of a 1 cm spot on the slide wasperformed. The slide was then transferred to a holder placed adjacent tothe solar simulator and, using a calipers, was positioned such that thebeam of UV radiation exiting the solar simulator illuminated the same 1cm spot on the slide. To test stability of a slide in the UV-A range,the PMA 2114 was substituted for the PMA 2105, and a WG335 filter wasinstalled in the beam path. The following software settings were used:UV-B =290-320 nm; UV-A=320-400 nm. Following an exposure of 5 MED, theslide was again placed in position on the UV transmittance analyzer, anda scan of the exposed spot was performed. The procedure was repeated onthe same 1 cm spot on the slide until the desired total radiation dosagewas achieved (approximately 35 MED for the UV-B studies, and 120 J/cm²for the UV-A studies).

FIG. 2 is a graph of the absorbance of the composition listed in TableII and the sunscreen compositions listed in Table III. As shown in FIG.2, the sunscreen composition that does includes 2% of theOctadecene/Crylene maleate copolymer achieves the highest absorbance ascompared to the sunscreen composition of Table III that does not includethe polymer and the composition of Table II that includes 2% of thepolymer as the only UV-absorber.

FIG. 3 is a graph of the absorbance of the sunscreen composition listedin Table III, which has no Octadecene/Crylene maleate copolymer in thecomposition. The absorbance spectra of the composition was recordedbefore and after exposure to 35 MED of radiation. As shown in FIG. 3,the sunscreen composition that does not include the Octadecene/Crylenemaleate copolymer is susceptible to photodegradation at 35 MED exposure.

FIG. 4 is a graph of the absorbance of the sunscreen composition listedin Table III that includes 2% of the Octadecene/Crylene maleatecopolymer in the composition. The absorbance spectra of the compositionwas recorded before and after exposure to 35 MED of radiation. As shownin FIG. 4, the absorbance spectra of the sunscreen composition of TableIII that includes 2% of the Octadecene/Crylene maleate copolymer showsthat the composition is relatively stable to photodegradation uponexposure to up to 35 MED.

FIG. 5 is a graph of the absorbance of the both sunscreen compositionslisted in Table III, including one that includes 2% of theOctadecene/Crylene maleate copolymer, and one that does not include theOctadecene/Crylene maleate copolymer. The absorbance spectra ofcompositions were recorded before and after exposure to 35 MED ofradiation. As shown in FIG. 4, the Octadecene/Crylene maleate copolymerincreases the photostability of the composition.

FIGS. 6 and 7 are the absorbance spectra for the compositions listed inTable III.

Example 4

A determination of the Sun Protection Factor (SPF) of the sunscreencompositions listed in Table II and Table III was performed. To test theSPF of the compositions, each slide was placed on the UV transmittanceanalyzer and scans were taken from five locations on the slide. An SPFreport was generated for each slide using the Labsphere softwareUV1000S, Version 1.27.

The results of the SPF testing for the composition listed in Table IIand the compositions listed in Table III are shown below in Table IV:TABLE IV Composition SPF Results Composition with 2% Scan No. 1 4.65Polymer as the only UV- Scan No. 2 4.68 Absorbing Compound Scan No. 35.04 (Table II) Scan No. 4 5.17 Scan No. 5 4.89 Average SPF 4.9Sunscreen Composition Scan No. 1 23.32 with 0% Polymer Scan No. 2 21.98(Table III) Scan No. 3 18.96 Scan No. 4 23.35 Scan No. 5 21.88 AverageSPF 21.9 Sunscreen Composition Scan No. 1 25.78 with 2% Polymer Scan No.2 27.90 (Table III) Scan No. 3 26.96 Scan No. 4 27.64 Scan No. 5 25.83Average SPF 26.8

The results shown in Table IV indicate that the addition of 2%Octadecene/Crylene maleate copolymer to a topical composition thecontains no other UV absorbers provides an SPF of about 5, and providesan increase in SPF of about 5 to sunscreen compositions.

Example 5

The water resistance of sunscreen compositions listed in Table III wastested by immersing slides of VITRO-SKIN, which contain thecompositions, in moving water for a period of time and testing theslides for a loss in absorbance as measured by SPF. The slides weretested before and after being immersed in water and the results werecompared.

The slides were prepared according to the procedure set forth in Example3, and each slide was placed in a beaker and the top, bottom, and sidesof the slides were secured in the beaker with binder clips. The slideswere then completely immersed in water by the addition of two liters oftap water to the beaker. The beaker was placed on a stir table and astir bar is placed on the bottom of the beaker. The stir bar is set inmotion to circulate the water with a mild vortex. After 40 minutes, theslides were removed from the beaker, shaken to remove excess water, andallowed to air-dry for 30 minutes. Scans are taken from five locationson the slides. The absorbance spectra and an SPF report was generatedfor each composition.

The results of the SPF reports are summarized in Table V below: TABLE VPre-Immersion Post-Immersion Composition SPF Results SPF ResultsSunscreen Composition Scan No. 1 23.58 12.10 with 0% Polymer Scan No. 222.39 10.73 (Table III) Scan No. 3 19.81 9.69 Scan No. 4 24.11 12.57Scan No. 5 21.17 11.07 Average SPF 22.2 11.2 Sunscreen Composition ScanNo. 1 27.09 29.08 with 2% Polymer Scan No. 2 27.77 29.45 (Table III)Scan No. 3 27.23 29.10 Scan No. 4 27.29 29.42 Scan No. 5 27.74 28.30Average SPF 27.4 29.1

As shown in Table V, the immersion of the sunscreen compositioncontaining 0% of the Octadecene/Crylene maleate copolymer in watercauses a significant loss of SPF. In contrast, when the sunscreencomposition listed in Table III that included 2% Octadecene/Crylenemaleate copolymer was immersed in water, there was actually a slightincrease in the SPF results as compared to the pre-immersion SPFresults. We consider this increase to be anomalous and withoutsignificance. However, this test and the others referenced in theaccompanying demonstrate the polymer's ability to: (a) provide waterresistance (i.e., water proofing) to the composition, and therebyavoiding loss of the composition upon immersion; (2) absorbUV-radiation; and (3) stabilize the other photoactive compounds in thecomposition by, for example, absorbing the excited state energy of otherphotoactive compounds and rapidly dissipating that energy.

FIG. 8 is a graph of the absorbance of the sunscreen composition listedin Table III where there is no Octadecene/Crylene maleate copolymer inthe composition. As shown in FIG. 8, there is a significant loss inabsorbance after the composition has been immersed in moving water for40 minutes.

FIG. 9 is a graph of the absorbance of the sunscreen composition listedin Table III that included 2% Octadecene/Crylene maleate copolymer inthe composition. As shown in FIG. 9, the absorbance spectra indicatesthat the immersion of the composition in moving water for 40 minutesdoes not cause a loss in the absorbance over the entire UV-spectra(290-400 nm).

FIG. 10 is a graph of the percent absorbance of both of the sunscreencompositions listed in Table III. As shown in FIG. 10, as compared tothe composition that does not include the Octadecene/Crylene maleatecopolymer, the addition of the Octadecene/Crylene maleate copolymer tothe composition prevents a loss in absorbance upon immersion in movingwater for 40 minutes.

The foregoing description is given for clearness of understanding only,and no unnecessary limitations should be understood therefrom, asmodifications within the scope of the compounds, compositions, andmethods disclosed herein may be apparent to those having ordinary skillin the art.

1. A compound of formula (I):

wherein R¹, R², R³, R^(4,)R⁵, and R⁶ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, e, g, f, and h are eachin the range of 0 to 4, m and n are each in the range of 0 to 5000, andthe sum of m plus n is at least
 1. 2. The compound of claim 1, whereinR¹ and R² are selected from the group consisting of C₁-C₃₀ alkyl groups.3. The compound of claim 2, wherein R¹ is a C₁₆ straight chain alkylgroup, and R² is a 2,2-dimethylpropyl group.
 4. The compound of claim 1,wherein the Weight-Average Molecular Weight of said compound is in therange of about 30,000 to about 110,000.
 5. A compound of formula (II):

wherein R⁷, R⁸, R⁹, and R¹⁰ are the same or different and selected fromthe group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl,heterocycloalkyl, substituted aryl, substituted heteroaryl, substitutedheterocycloalkyl, cyano, and amino, i, j, k, and l are each in the rangeof 0 to 4, o and p are each in the range of 0 to 5000, and the sum of oplus p is at least
 1. 6. The compound of claim 5, wherein theWeight-Average Molecular Weight of said compound is in the range ofabout 30,000 to about 110,000.
 7. The product of the reaction betweenthe polymer of formula (III) and a compound selected from the groupconsisting of compounds of formulae (IV), (V), and combinations thereof:

wherein R¹¹, R¹², R¹³, R¹⁴, and R³⁹ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, m, n, o, and p are eachin the range of 0 to 4, and q is in the range of 2 to
 5000. 8. Theproduct of claim 7, wherein, wherein R³⁹ is selected from groupconsisting of C₁-C₃₀ alkyl groups.
 9. The product of claim 8, wherein,wherein R³⁹ is a C₁₆ straight chain alkyl group.
 10. The product ofclaim 7, wherein the Weight-Average Molecular Weight of said product isin the range of about 30,000 to about 110,000.
 11. A sunscreencomposition, comprising a mixture of a photoactive compound, and acompound of formula (I):

wherein R¹, R², R³, R^(4,)R⁵, and R⁶ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, e, g, f, and h are eachin the range of 0 to 4, m and n are each in the range of 0 to 5000, andthe sum of m plus n is at least
 1. 12. The composition of claim 11,wherein R¹ and R² are selected from the group consisting of C₁-C₃₀ alkylgroups.
 13. The composition of claim 12, wherein R¹ is a C₁₆ straightchain alkyl group, and R² is a 2,2-dimethylpropyl group.
 14. Thecomposition of claim 11, wherein said compound of formula (I) is presentsaid composition in an amount in the range of about 0.01% to about 30%by weight of the total weight of the composition.
 15. The composition ofclaim 11, further comprising a diester or polyester of naphthalenedicarboxylic acid selected from the group consisting of compounds offormulae (XIII) and (XIV), and combinations thereof:

wherein R⁴³ and R⁴⁴ are the same or different and selected from thegroup consisting of C₁-C₂₂ alkyl groups, diols having the structureHO—R⁴¹—OH, and polyglycols having the structure HO—R⁴⁰—(—O—R⁴¹—)_(j)—OH;wherein each R⁴⁰ and R⁴¹ is the same or different and selected from thegroup consisting of C₁-C₆ straight or branched chain alkyl groups; andwherein h and j are each in a range of 1 to 100 and i is in a range of 0to
 100. 16. A method of protecting human skin from ultraviolet radiationcomprising topically applying to said skin, in a cosmetically acceptablecarrier, the composition of claim
 11. 17. A method of protecting humanskin from ultraviolet radiation, comprising topically applying to saidskin, in a cosmetically acceptable carrier, a compound of formula (I):

wherein R¹, R², R³, R^(4,)R⁵, and R⁶ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, e, g, f, and h are eachin the range of 0 to 4, m and n are each in the range of 0 to 5000, andthe sum of m plus n is at least
 1. 18. The method of claim 17, whereinR¹ and R² are selected from the group consisting of C₁-C₃₀ alkyl groups.19. The method of claim 18, wherein R¹ is a C₁₆ straight chain alkylgroup, and R² is a 2,2-dimethylpropyl group.
 20. A method ofwaterproofing a surface, comprising applying a compound of formula (I)to a selected area of said surface:

wherein R¹, R², R³, R^(4,)R⁵, and R⁶ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, e, g, f, and h are eachin the range of 0 to 4, m and n are each in the range of 0 to 5000, andthe sum of m plus n is at least
 1. 21. The method of claim 20, whereinR¹ and R² are selected from the group consisting of C₁-C₃₀ alkyl groups.22. The method of claim 21, wherein R¹ is a C₁₆ straight chain alkylgroup, and R² is a 2,2-dimethylpropyl group.
 23. A method of protectinga selected area of a material from photodegradation, comprising applyinga compound of formula (I) to said selected area of said material:

wherein R¹, R², R³, R^(4,)R⁵, and R⁶ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, e, g, f, and h are eachin the range of 0 to 4, m and n are each in the range of 0 to 5000, andthe sum of m plus n is at least
 1. 24. The method of claim 23, whereinR¹ and R² are selected from the group consisting of C₁-C₃₀ alkyl groups.25. The method of claim 24, wherein R¹ is a C₁₆ straight chain alkylgroup, and R² is a 2,2-dimethylpropyl group.
 26. A method for forming afilm over at least part of a surface, comprising spreading a compound offormula (I) on said part of said surface:

wherein R¹, R², R³, R^(4,)R⁵, and R⁶ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, e, g, f, and h are eachin the range of 0 to 4, m and n are each in the range of 0 to 5000, andthe sum of m plus n is at least
 1. 27. The method of claim 26, whereinR¹ and R² are selected from the group consisting of C₁-C₃₀ alkyl groups.28. The method of claim 27, wherein R¹ is a C₁₆ straight chain alkylgroup, and R² is a 2,2-dimethylpropyl group.
 29. A method ofphotostabilizing a dibenzoylmethane derivative, said method comprisingthe step of, adding to said dibenzoylmethane derivative aphotostabilizing amount of a compound of formula (I):

wherein R¹, R², R³, R^(4,)R⁵, and R⁶ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, e, g, f, and h are eachin the range of 0 to 4, m and n are each in the range of 0 to 5000, andthe sum of m plus n is at least
 1. 30. The method of claim 29, whereinR¹ and R² are selected from the group consisting of C₁-C₃₀ alkyl groups.31. The method of claim 30, wherein R¹ is a C₁₆ straight chain alkylgroup, and R² is a 2,2-dimethylpropyl group.
 32. The method of claim 29,further comprising the step of, adding to said dibenzoylmethanederivative a diester or polyester of naphthalene dicarboxylic acidselected from the group consisting of compounds of formulae (XIII) and(XIV), and combinations thereof:

wherein R⁴³ and R⁴⁴ are the same or different and selected from thegroup consisting of C₁-C₂₂ alkyl groups, diols having the structureHO—R⁴¹—OH, and polyglycols having the structure HO—R⁴⁰—(—O—R⁴¹—)_(j)—OH;wherein each R⁴⁰ and R⁴¹ is the same or different and selected from thegroup consisting of C₁-C₆ straight or branched chain alkyl groups; andwherein h and j are each in a range of 1 to 100 and i is in a range of 0to
 100. 33. A compound of formula (VI):

wherein R³, R^(4,)R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, s, t, u, and v are eachin the range of 0 to 4, q and r are each in the range of 0 to 5000, andthe sum of q plus r is at least
 1. 34. The compound of claim 33, whereinR³ and R⁴ are selected from the group consisting of C₁-C₃₀ alkyl groups.35. The compound of claim 34, wherein R³ is a C₁₆ straight chain alkylgroup, and R⁴ is a 2,2-dimethylpropyl group.
 36. The compound of claim33, wherein the Weight-Average Molecular Weight of said compound is inthe range of about 30,000 to about 10,000.
 37. A compound of formula(VII):

wherein R¹⁹, R²⁰, R²¹, and R²² are the same or different and selectedfrom the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl,C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl,heterocycloalkyl, substituted aryl, substituted heteroaryl, substitutedheterocycloalkyl, cyano, and amino, w, x, y, and z are each in the rangeof 0 to 4, s and t are each in the range of 0 to 5000, and the sum of splus t is at least
 1. 38. The compound of claim 37, wherein theWeight-Average Molecular Weight of said compound is in the range ofabout 30,000 to about 110,000.
 39. A sunscreen composition, comprising amixture of a photoactive compound, and a compound of formula (VI):

wherein R³, R⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, s, t, u, and v are eachin the range of 0 to 4, q and r are each in the range of 0 to 5000, andthe sum of q plus r is at least
 1. 40. The composition of claim 39,wherein R³ and R⁴ are selected from the group consisting of C₁-C₃₀ alkylgroups.
 41. The composition of claim 40, wherein R³ is a C₁₆ straightchain alkyl group, and R⁴ is a 2,2-dimethylpropyl group.
 42. Thecomposition of claim 39, wherein said compound of formula (VI) ispresent said composition in an amount in the range of about 0.01% toabout 30% by weight of the total weight of the composition.
 43. Thecomposition of claim 39, further comprising a diester or polyester ofnaphthalene dicarboxylic acid selected from the group consisting ofcompounds of formulae (XIII) and (XIV), and combinations thereof:

wherein R⁴³ and R⁴⁴ are the same or different and selected from thegroup consisting of C₁-C₂₂ alkyl groups, diols having the structureHO—R⁴¹—OH, and polyglycols having the structure HO—R⁴⁰—(—O—R⁴¹—)_(j)—OH;wherein each R⁴⁰ and R⁴¹ is the same or different and selected from thegroup consisting of C₁-C₆ straight or branched chain alkyl groups; andwherein h and j are each in a range of 1 to 100 and i is in a range of 0to
 100. 44. A method of protecting human skin from ultraviolet radiationcomprising topically applying to said skin, in a cosmetically acceptablecarrier, the composition of claim
 39. 45. A method of protecting humanskin from ultraviolet radiation, comprising topically applying to saidskin, in a cosmetically acceptable carrier, a compound of formula (VI):

wherein R³, R⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, s, t, u, and v are eachin the range of 0 to 4, q and r are each in the range of 0 to 5000, andthe sum of q plus r is at least
 1. 46. The method of claim 45, whereinR³ and R⁴ are selected from the group consisting of C₁-C₃₀ alkyl groups.47. The method of claim 46, wherein R³ is a C₁₆ straight chain alkylgroup, and R⁴ is a 2,2-dimethylpropyl group.
 48. A method ofwaterproofing a surface, comprising applying a compound of formula (VI)to a selected area of said surface:

wherein R³, R⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, s, t, u, and v are eachin the range of 0 to 4, q and r are each in the range of 0 to 5000, andthe sum of q plus r is at least
 1. 49. The method of claim 48, whereinR³ and R⁴ are selected from the group consisting of C₁-C₃₀ alkyl groups.50. The method of claim 49, wherein R³ is a C₁₆ straight chain alkylgroup, and R⁴ is a 2,2-dimethylpropyl group.
 51. A method of protectinga selected area of a material from photodegradation, comprising applyinga compound of formula (VI) to said selected area of said material:

wherein R³, R⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, s, t, u, and v are eachin the range of 0 to 4, q and r are each in the range of 0 to 5000, andthe sum of q plus r is at least
 1. 52. The method of claim 5 1, whereinR³ and R⁴ are selected from the group consisting of C₁-C₃₀ alkyl groups.53. The method of claim 52, wherein R³ is a C₁₆ straight chain alkylgroup, and R⁴ is a 2,2-dimethylpropyl group.
 54. A method for forming afilm over at least part of a surface, comprising spreading a compound offormula (VI) on said part of said surface:

wherein R³, R⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, s, t, u, and v are eachin the range of 0 to 4, q and r are each in the range of 0 to 5000, andthe sum of q plus r is at q least
 1. 55. The method of claim 54, whereinR³ and R⁴ are selected from the group consisting of C₁-C₃₀ alkyl groups.56. The method of claim 55, wherein R³ is a C₁₆ straight chain alkylgroup, and R⁴ is a 2,2-dimethylpropyl group.
 57. A method ofphotostabilizing a dibenzoylmethane derivative, said method comprisingthe step of, adding to said dibenzoylmethane derivative aphotostabilizing amount of a compound of formula (VI):

wherein R³, R⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ are the same or different andselected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀ substitutedalkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl, ester, aryl,heteroaryl, heterocycloalkyl, substituted aryl, substituted heteroaryl,substituted heterocycloalkyl, cyano, and amino, s, t, u, and v are eachin the range of 0 to 4, q and r are each in the range of 0 to 5000, andthe sum of q plus r is at least
 1. 58. The method of claim 57, whereinR³ and R⁴ are selected from the group consisting of C₁-C₃₀ alkyl groups.59. The method of claim 58, wherein R³ is a C₁₆ straight chain alkylgroup, and R⁴ is a 2,2-dimethylpropyl group.
 60. The method of claim 57,further comprising the step of, adding to said dibenzoylmethanederivative a diester or polyester of naphthalene dicarboxylic acidselected from the group consisting of compounds of formulae (XIII) and(XIV), and combinations thereof:

wherein R⁴³ and R⁴⁴ are the same or different and selected from thegroup consisting of C₁-C₂₂ alkyl groups, diols having the structureHO—R⁴¹—OH, and polyglycols having the structure HO—R⁴⁰—(—O—R⁴¹—)_(j)—OH;wherein each R⁴⁰ and R⁴¹ is the same or different and selected from thegroup consisting of C₁-C₆ straight or branched chain alkyl groups; andwherein h and j are each in a range of 1 to 100 and i is in a range of 0to
 100. 61. A compound of formula (IX):

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵,R³⁶, R³⁷, and R³⁸ are the same or different and selected from the groupconsisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈ cycloalkyl,C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl, heterocycloalkyl,substituted aryl, substituted heteroaryl, substituted heterocycloalkyl,cyano, and amino, e, f, h, i, j, k, l, and m are each in the range of 0to 4, a, b, c, and d are each in the range of 0 to 5000, and the sum ofa, b, c, and d is at least
 1. 62. The compound of claim 61, wherein R²³,R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, and R³⁰ are selected from the groupconsisting of C₁-C₃₀ alkyl groups.
 63. The compound of claim 62, whereinR²³, R²⁴, R²⁵, R²⁶ are C₁₆ straight chain alkyl groups, and R²⁷, R²⁸,R²⁹, and R³⁰ are 2,2-dimethylpropyl groups.
 64. The compound of claim61, wherein the Weight-Average Molecular Weight of said compound is inthe range of about 30,000 to about 110,000.
 65. A compound of formula(X):

wherein R³⁹, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ are the same ordifferent and selected from the group consisting of C₁-C₃₀ alkyl, C₁-C₃₀substituted alkyl, C₃-C₈ cycloalkyl, C₃-C₈ substituted cycloalkyl,ester, aryl, heteroaryl, heterocycloalkyl, substituted aryl, substitutedheteroaryl, substituted heterocycloalkyl, cyano, and amino, r, s, t, u,v, w, x, and y are each in the range of 0 to 4, n, o, p, and q are eachin the range of 0 to 5000, and the sum of n, o, p, and q is at least 1.66. The compound of claim 65, wherein the Weight-Average MolecularWeight of said compound is in the range of about 30,000 to about110,000.
 67. A sunscreen composition, comprising a mixture of aphotoactive compound, and a compound of formula (IX):

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵,R³⁶, R³⁷, and R³⁸ are the same or different and selected from the groupconsisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈ cycloalkyl,C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl, heterocycloalkyl,substituted aryl, substituted heteroaryl, substituted heterocycloalkyl,cyano, and amino, e, f, h, i, j, k, l, and m are each in the range of 0to 4, a, b, c, and d are each in the range of 0 to 5000, and the sum ofa, b, c, and d is at least
 1. 68. The composition of claim 67, whereinR²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, and R³⁰ are selected from the groupconsisting of C₁-C₃₀ alkyl groups.
 69. The composition of claim 68,wherein R²³, R²⁴, R²⁵, R²⁶ are C₁₆ straight chain alkyl groups, and R²⁷,R²⁸, R²⁹, and R³⁰ are 2,2-dimethylpropyl groups.
 70. The composition ofclaim 67, wherein said compound of formula (IX) is present saidcomposition in an amount in the range of about 0.01% to about 30% byweight of the total weight of the composition.
 71. The composition ofclaim 67, further comprising a diester or polyester of naphthalenedicarboxylic acid selected from the group consisting of compounds offormulae (XIII) and (XIV), and combinations thereof:

wherein R⁴³ and R⁴⁴ are the same or different and selected from thegroup consisting of C₁-C₂₂ alkyl groups, diols having the structureHO—R⁴¹—OH, and polyglycols having the structure HO—R⁴⁰—(—O—R⁴¹—)_(j)—OH;wherein each R⁴⁰ and R⁴¹ is the same or different and selected from thegroup consisting of C₁-C₆ straight or branched chain alkyl groups; andwherein h and j are each in a range of 1 to 100 and i is in a range of 0to
 100. 72. A method of protecting human skin from ultraviolet radiationcomprising topically applying to said skin, in a cosmetically acceptablecarrier, the composition of claim
 67. 73. A method of protecting humanskin from ultraviolet radiation, comprising topically applying to saidskin, in a cosmetically acceptable carrier, a compound of formula (IX):

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵,R³⁶, R³⁷, and R³⁸ are the same or different and selected from the groupconsisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈ cycloalkyl,C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl, heterocycloalkyl,substituted aryl, substituted heteroaryl, substituted heterocycloalkyl,cyano, and amino, e, f, h, i, j, k, l, and m are each in the range of 0to 4, a, b, c, and d are each in the range of 0 to 5000, and the sum ofa, b, c, and d is at least
 1. 74. The method of claim 73, wherein R²³,R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, and R³⁰ are selected from the groupconsisting of C₁-C₃₀ alkyl groups.
 75. The method of claim 74, whereinR²³, R²⁴, R²⁵, R²⁶ are C₁₆ straight chain alkyl groups, and R²⁷, R²⁸,R²⁹, and R³⁰ are 2,2-dimethylpropyl groups.
 76. A method ofwaterproofing a surface, comprising applying a compound of formula (IX)to a selected area of said surface:

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵,R³⁶, R³⁷, and R³⁸ are the same or different and selected from the groupconsisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈ cycloalkyl,C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl, heterocycloalkyl,substituted aryl, substituted heteroaryl, substituted heterocycloalkyl,cyano, and amino, e, f, h, i, j, k, l, and m are each in the range of 0to 4, a, b, c, and d are each in the range of 0 to 5000, and the sum ofa, b, c, and d is at least
 1. 77. The method of claim 76, wherein R²³,R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, and R³⁰ are selected from the groupconsisting of C₁-C₃₀ alkyl groups.
 78. The method of claim 77, whereinR²³, R²⁴, R²⁵, R²⁶ are C₁₆ straight chain alkyl groups, and R²⁷, R²⁸,R²⁹, and R³⁰ are 2,2-dimethylpropyl groups.
 79. A method of protecting aselected area of a material from photodegradation, comprising applying acompound of formula (IX) to said selected area of said material:

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵,R³⁶, R³⁷, and R³⁸ are the same or different and selected from the groupconsisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈ cycloalkyl,C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl, heterocycloalkyl,substituted aryl, substituted heteroaryl, substituted heterocycloalkyl,cyano, and amino, e, f, h, i, j, k, l, and m are each in the range of 0to 4, a, b, c, and d are each in the range of 0 to 5000, and the sum ofa, b, c, and d is at least
 1. 80. The method of claim 77, wherein R²³,R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, and R³⁰ are selected from the groupconsisting of C₁-C₃₀ alkyl groups.
 81. The method of claim 80, whereinR²³, R²⁴, R²⁵, R²⁶ are C₁₆ straight chain alkyl groups, and R²⁷, R²⁸,R²⁹, and R³⁰ are 2,2-dimethylpropyl groups.
 82. A method for forming afilm over at least part of a surface, comprising spreading a compound offormula (IX) on said part of said surface:

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵,R³⁶, R³⁷, and R³⁸ are the same or different and selected from the groupconsisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈ cycloalkyl,C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl, heterocycloalkyl,substituted aryl, substituted heteroaryl, substituted heterocycloalkyl,cyano, and amino, e, f, h, i, j, k, l, and m are each in the range of 0to 4, a, b, c, and d are each in the range of 0 to 5000, and the sum ofa, b, c, and d is at least
 1. 83. The method of claim 82, wherein R²³,R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, and R³⁰ are selected from the groupconsisting of C₁-C₃₀ alkyl groups.
 84. The method of claim 83, whereinR²³, R²⁴, R²⁵, R²⁶ are C₁₆ straight chain alkyl groups, and R²⁷, R²⁸,R²⁹, and R³⁰ are 2,2-dimethylpropyl groups.
 85. A method ofphotostabilizing a dibenzoylmethane derivative, said method comprisingthe step of, adding to said dibenzoylmethane derivative aphotostabilizing amount of a compound of formula (IX):

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵,R³⁶, R³⁷, and R³⁸ are the same or different and selected from the groupconsisting of C₁-C₃₀ alkyl, C₁-C₃₀ substituted alkyl, C₃-C₈ cycloalkyl,C₃-C₈ substituted cycloalkyl, ester, aryl, heteroaryl, heterocycloalkyl,substituted aryl, substituted heteroaryl, substituted heterocycloalkyl,cyano, and amino, e, f, h, i, j, k, l, and m are each in the range of 0to 4, a, b, c, and d are each in the range of 0 to 5000, and the sum ofa, b, c, and d is at least
 1. 86. The method of claim 85, wherein R²³,R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, and R³⁰ are selected from the groupconsisting of C₁-C₃₀ alkyl groups.
 87. The method of claim 86, whereinR²³, R²⁴, R²⁵, R²⁶ are C₁₆ straight chain alkyl groups, and R²⁷, R²⁸,R²⁹, and R³⁰ are 2,2-dimethylpropyl groups.
 88. The method of claim 85,further comprising the step of, adding to said dibenzoylmethanederivative a diester or polyester of naphthalene dicarboxylic acidselected from the group consisting of compounds of formulae (XIII) and(XIV), and combinations thereof:

wherein R⁴³ and R⁴⁴ are the same or different and selected from thegroup consisting of C₁-C₂₂ alkyl groups, diols having the structureHO—R⁴¹—OH, and polyglycols having the structure HO—R⁴⁰—(—O—R⁴¹—)_(j)—OH;wherein each R⁴⁰ and R⁴¹ is the same or different and selected from thegroup consisting of C₁-C₆ straight or branched chain alkyl groups; andwherein h and j are each in a range of 1 to 100 and i is in a range of 0to 100.